Biphenyl derivatives and their use as fungicides

ABSTRACT

A fungicidally active compound of formula (1): where Het is a substituted 5- or 6-membered heterocyclic ring; R 1  is hydrogen, formyl, CO-C 1-4  alkyl, COO-C 1-4  alkyl, C 1-4  alkoxy(C 1-4 )alkylene, CO-C 1-4  alkylenoxy(C 1-4 )alkyl, propargyl or allenyl; R 2 , R 3 , R 4  and R 5  are each, independently, hydrogen, halogen, methyl or CF 3 ; each R 6  is, independently, halogen, methyl or CF 3 ; R 7  is (Z) m C═C(Y 1 ), (Z) m C(Y 1 )═C(Y 2 )(Y 3 ) or tri(C 1-4 )alkylsilyl; X is O or S; Y 1 , Y 2  and Y 3  are each, independently, hydrogen, halogen, C 1-6  alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, C 1-4  alkoxy, C 1-4  haloalkoxy, C 1-4  alkylthio, C 1-4  haloalkylthio, C 1-4  alkylamino, di(C 1-4 )alkylamino, C 1-4  alkoxycarbonyl, C 1-4  alkylcarbonyloxy and tri(C 1-4 )alkylsilyl], C 2-4  alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C 2-4  alkynyl [optionally substituted by one or more substituents each independently selected from halogen], C 3-7  cycloalkyl [optionally substituted by one or more substituents each independently selected from halogen, C 1-4  alkyl and C 1-4  haloalkyl] or tri(C 1-4 )alkylsilyl; Z is C 1-4  alkylene [optionally substituted by one or more substituents each independently selected from hydroxy, cyano, C 1-4  alkoxy, halogen, C 1-4  haloalkyl, C 1-4  haloalkoxy, C 1-4  alkylthio, COOH and COO-C 1-4  alkyl]; m is 0 or 1; and n is 0, 1 or 2; the invention also relates to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

The present invention relates to novel carboxamide derivatives as active ingredients which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these active ingredients, to novel diphenyl derivatives used as intermediates in the preparation of these active ingredients, to preparation of these novel intermediates, to agrochemical compositions which comprise at least one of the novel active ingredients, to preparation of these compositions and to use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Fungicidally active carboxamide derivatives are disclosed in JP2001072510, JP2001072508, JP2001072507 and JP2001302605.

Certain amino- or halo-substituted diphenyl derivatives are disclosed in DE2205732 and JP2001302605.

The present invention provides a compound of formula (I):

where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and suphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by one, two or three groups R^(y); R¹ is hydrogen, formyl, CO-C₁₋₄ alkyl, COO-C₁₋₄ alkyl, C₁₋₄ alkoxy(C₁₋₄)alkylene, CO-C₁₋₄ alkylenoxy(C₁₋₄)alkyl, propargyl or allenyl; R², R³, R⁴ and R⁵ are each, independently, hydrogen, halogen, methyl or CF₃; each R⁶ is, independently, halogen, methyl or CF₃; R⁷ is (Z)_(m)C≡C(Y¹), (Z)_(m)C(Y¹)═C(Y²)(Y³) or tri(C₁₋₄)alkylsilyl; each R^(y) is, independently, halogen, C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy(C₁₋₃)alkylene or cyano; X is 0 or S; Y¹, Y² and Y³ are each, independently, hydrogen, halogen, C₁₋₆ alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio, C₁₋₄ alkylamino, di(C₁₋₄)alkylamino, C₁₋₄ alkoxycarbonyl, C₁₋₄ alkylcarbonyloxy and tri(C₁₋₄)alkylsilyl], C₂₋₄ alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C₂₋₄ alkynyl [optionally substituted by one or more substituents each independently selected from halogen], C₃₋₇ cycloalkyl [optionally substituted by one or more substituents each independently selected from halogen, C₁₋₄ alkyl and C₁₋₄ haloalkyl] or tri(C₁₋₄)alkylsilyl; Z is C₁₋₄ alkylene [optionally substituted by one or more substituents each independently selected from hydroxy, cyano, C₁₋₄ alkoxy, halogen, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, COOH and COO-C₁₋₄ alkyl]; m is 0 or 1; and n is 0, 1 or 2.

In one particular aspect, the present invention provides a compound of formula (I) as defined above where Y¹, Y² and Y³ are each, independently, hydrogen, halogen, C₁₋₄ alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio, C₁₋₄ alkylamino, di(C₁₋₄)alkylamino, C₁₋₄ alkoxycarbonyl and tri(C₁₋₄)alkylsilyl], C₂₋₄ alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C₂₋₄ alkynyl [optionally substituted by one or more substituents each independently selected from halogen], C₃₋₇ cycloalkyl [optionally substituted by one or more substituents each independently selected from halogen, C₁₋₄ alkyl and C₁₋₄ haloalkyl] or tri(C₁₋₄)alkylsilyl.

In one aspect, the present invention provides a compound of formula (I) as defined above where Z is C₁₋₄ alkylene [optionally substituted by one or more substituents each independently selected from hydroxy, cyano, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, COOH and COO-C₁₋₄ alkyl].

In one aspect, the present invention provides a compound of formula (I) as defined above provided that R⁷ is not C₂₋₆ alkenyl when X is 0; R¹ is hydrogen; one of R², R³, R⁴ and R⁵ is fluorine and the others are all hydrogen; n is 1; and Het is

In another aspect, the present invention provides a compound of formula (I) as defined above provided that R⁷ is not C₂₋₆ alkenyl when X is 0; R¹, R², R³, R⁴ and R⁵ are all hydrogen; and Het is

In a further aspect, the present invention provides a compound of formula (I) as defined above provided that R⁷ is not C₂₋₆ alkenyl when X is 0; R¹, R², R³, R⁴ and R⁵ are all hydrogen; n is 1; and Het is

In yet another aspect, the present invention provides a compound of formula (I) as defined above provided that R⁷ is not C₂₋₆ alkenyl in the 4′ position when X is 0; R¹, R³ and R⁵ are all hydrogen; R² and R⁴ are each, independently, hydrogen or fluorine; n is 0; or n is 1; or n is 2 and the two independent R⁶ substituents are in positions 2′,3′ or 2′,5′ or 3′,5′; and Het is

Halogen is fluorine, chlorine, bromine or iodine [preferably fluorine, chlorine or bromine].

Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl. Likewise, each alkylene moiety is a straight or branched chain.

Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF₃, CF₂Cl, CHF₂, CH₂F, CCl₃, CF₃CH₂, CHF₂CH₂, CH₂FCH₂, CH₃CHF or CH₃CF₂.

Alkenyl and alkynyl moieties can be in the form of straight or branched chains. The alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl, allyl, ethynyl and propargyl.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

In tri(C₁₋₄)alkylsilyl and in di(C₁₋₄)alkylamino, each alkyl moiety is selected independently.

Throughout this description, Me stands for methyl and Et stands for ethyl.

It is preferred that Het is pyrazole, pyrrole, thiophene, furan, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 5,6-dihydropyran or 5,6-dihydro-1,4-oxathiine [more preferably pyrazole, pyrrole, thiophene, furan, thiazole, oxazole, pyridine, pyrimidine, pyridazine or 5,6-dihydropyran; yet more preferably pyrazole, pyrrole, pyridine or thiazole; and even more preferably pyrazole, pyrrole or thiazole].

In one aspect it is preferred that Het is pyrazole, pyrrole, thiophene, furan, thiazole, isothiazole, oxazole, isoxazole, pyrazine, pyrimidine, pyridazine, 5,6-dihydropyran or 5,6-dihydro-1,4-oxathiine [more preferably pyrazole, pyrrole, thiophene, furan, thiazole, oxazole, pyrimidine, pyridazine or 5,6-dihydropyran and even more preferably pyrazole, pyrrole or thiazole].

Preferably R¹ is hydrogen, propargyl, allenyl, formyl, COMe, COEt or COCH₂OMe.

More preferably R¹ is hydrogen.

Preferably R² is hydrogen.

Preferably R³ is hydrogen.

Preferably R⁴ is hydrogen.

Preferably R⁵ is hydrogen or halogen.

More preferably R⁵ is hydrogen or fluorine.

Even more preferably R⁵ is hydrogen.

In one aspect of the invention R⁷ is tri(C₁₋₄)alkylsilyl.

Preferably Y¹, Y² and Y³ are, independently, hydrogen, halogen, C₁₋₆ alkyl, C₁₋₃ haloalkyl, C₁₋₄(haloalkoxy)C₁₋₄alkyl, C₁₋₄(haloalkylthio)C₁₋₄ alkyl, trimethylsilyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl or C₃₋₄ cycloalkyl (optionally substituted by one or more substituents each independently selected from halogen and C₁₋₂ alkyl).

Preferably Z is C₁₋₂ alkylene [which may be optionally substituted by one or more substituents each independently selected from halogen, C₁₋₄ haloalkyl and C₁₋₄ haloalkoxy].

Preferably R⁷ is in the 4′ position.

Preferably R⁷ is vinyl [optionally substituted by one to three substituents each independently selected from halogen, C₁₋₄ alkyl, C₁₋₃ haloalkyl, C₃₋₆ cycloalkyl (optionally substituted by one to five substituents each independently selected from halogen, CH₃ and C₁₋₂haloalkyl) and trimethylsilyl], ethynyl [optionally substituted by one substituent selected from cyclopropyl, cyclopentyl and cyclohexyl (each optionally substituted by one to five substituents each independently selected from halogen, CH₃ and C₁₋₂ haloalkyl), halogen, C₁₋₆ alkyl, C₁₋₄ haloalkyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl and tri(C₁₋₄)alkylsilyl], allyl [optionally substituted by one to three substituents each independently selected from halogen, CH₃, C₁₋₂ haloalkyl and trimethylsilyl], propargyl [optionally substituted by one to three substituents each independently selected from halogen, C₁₋₄ alkyl, C₁₋₂ haloalkyl and trimethylsilyl] or tri(C₁₋₄)alkylsilyl.

In one particular aspect R⁷ is preferably vinyl [optionally substituted by one to three substituents each independently selected from halogen, C₁₋₄ alkyl, C₁₋₃ haloalkyl, C₃₋₆ cycloalkyl and trimethylsilyl], ethynyl [optionally substituted by one substituent selected from halogen, C₁₋₄ alkyl, C₁₋₂ haloalkyl, cyclopropyl (optionally substituted by one to five substituents each independently selected from halogen, CH₃, C₁₋₂ haloalkyl and trimethylsilyl) and trimethylsilyl], allyl [optionally substituted by one to three substituents each independently selected from halogen, CH₃, C₁₋₂ haloalkyl and trimethylsilyl], propargyl [optionally substituted by one to three substituents each independently selected from halogen, CH₃, C₁₋₂ haloalkyl and trimethylsilyl] or tri(C₁₋₄)alkylsilyl.

In another particular aspect R⁷ is preferably vinyl [optionally substituted by one to three substituents each independently selected from halogen, C₁₋₄ alkyl, C₁₋₃ haloalkyl, C₃₋₆ cycloalkyl and trimethylsilyl], ethynyl [optionally substituted by one substituent selected from halogen, C₁₋₄ alkyl, C₁₋₂ haloalkyl and trimethylsilyl], allyl [optionally substituted by one to three substituents each independently selected from halogen, CH₃, C₁₋₂ haloalkyl and trimethylsilyl], propargyl [optionally substituted by one to three substituents each independently selected from halogen, CH₃, C₁₋₂ haloallyl and trimethylsilyl] or tri(C₁₋₄)alkylsilyl.

More preferably R⁷ is CH═CH₂, CH═CH(CH₃), CH═CHSiMe₃, CH═CF₂, CH═CCl₂, C(CH₃)═CCl₂, CH═CBr₂, C(CH₃)═CBr₂, C(CH₃)═CF₂, CH═CFCl, CH═CFBr, C(CH₃)═CFCl, C(CH₃)═CFBr, CH═CFMe, CH═CBrMe, CH═CClMe, CH═CHBr, CH═CHF, CH═CHCl, CF═CF₂, CCl═CF₂, CCl═CH₂, CBr═CH₂, CF═CH₂, C(CF₃)═CFBr, C(CF₃)═CFCl, C(CF₃)═CBr₂, C(CF₃)═CCl₂, C(CF₃)═CF₂, C(CF₃)═CH₂, CF═CHF, CH═CHCF₃, CH═CFCF₂Cl, CH═CCl, CF₂Cl, CH═CBrCF₂Cl, CH═C(CF₃)₂, CH═CHC₂F₅, CH═CHCF(CF₃)₂, C(CH₃)═CHCF₃, C(CH₃)═CFCF3, C(CH₃)═CClCF₃, C(CH₃)═CBrCF₃, CH═CClCF₃, CH═CClC₂F₅, CH═CBrCF₃, CH═CFC₂F₅, CH═CFCF₃, CH₂CH═CH₂, CH₂CH═CF₂, CH₂CH═CCl₂, CH₂CH═CBr₂, CH₂CH═CFBr, CH₂CH═CFCl, CH₂CH═CClCF₃, CH₂CH═CHSiMe₃, C≡CH, C≡CSiMe₃, C≡CSiEt₃, C≡CSiMe₂C(CH₃)₃, C≡CCl, C≡CBr, C—CF, C≡CCF₃, C≡CCF₂H, C≡CCF₂Cl, C≡CCF₂Me, C≡CCF₂Et, C≡CCHFCl, C≡CCF₂Br, C═CC₂F₅, C≡CCF(CF₃)₂, C═CCHF(CF₃), C═CCH₂F, C≡CCH(Me)F, C≡CCH(Et)F, C≡CMe, C═CCH₂Me, C≡CCHMe₂, C≡CCH₂CHMe₂, C≡CCMe₃, C≡CCH₂CMe₃, C≡CCH₂SiMe₃, C≡CCMe₂Cl, C≡CCMe₂F, C≡CCH₂OMe, C≡CCH₂CF₃, C≡CCMe₂OMe, C≡CCMe₂OH, C≡CCMe₂OCOMe, C≡CC(Me)═CH₂, C≡CCF═CF₂, C≡C(cyclopropyl), C≡C(cyclopentyl), C≡C(1-F-cyclopentyl), CH₂C≡CH, CF₂C≡CH, CHFC—CH, CH(CF₃)C≡CH, SiMe₃, CH₂C≡CCMe₃ or CH₂C≡CSiMe₃.

In one particular aspect R⁷ is more preferably CH═CH₂, CH═CH(CH₃), CH═CHSiMe₃, CH═CF₂, CH═CCl₂, C(CH₃)═CCl₂, CH═CBr₂, CF═CF₂, CCl═CH₂, CBr═CH₂, CF═CH₂, CF═CHF, CH═CHCF₃, CH═CClCF₃, CH═CBrCF₃, CH₂CH═CH₂, CH₂CH═CHSiMe₃, Cz═CH, C≡CSiMe₃, C≡CSiEt₃, C≡CSiMe₂C(CH₃)₃, C≡CCl, C≡CBr, C≡CCF₃, C≡CCF₂H, C≡CCF₂Cl, C≡CCF₂Br, CECCF(CF₃)₂C≡CMe, C≡CCHMe₂, C≡CCMe₃, C≡CCMe₂Cl, C≡CCH₂OMe, C≡C(cycloC₃H₅), C≡C(cycloC₅H₉), CH₂C≡CH, SiMe₃ or CH₂C≡CSiMe₃.

Even more preferably R⁷ is CH═CF₂, CH═CCl₂, C(CH₃)═CCl₂, CH═CBr₂, C(CH₃)═CBr₂, C(CH₃)═CF₂, CH═CFCl, CH═CFBr, C(CH₃)═CFCl, C(CH₃)═CFBr, CH═CHBr, CH═CHF, CH═CHCl, CCl═CH₂, CH═CHCF₃, CH═CFCF₂Cl, CH═CClCF₂Cl, CH═CBrCF₂Cl, CH═C(CF₃)₂, CH═CHC₂F₅, CH═CHCF(CF₃)₂, C(CH₃)═CHCF₃, CH═CClCF₃, CH═CClC₂F₅, CH═CFC₂F₅, CH═CBrCF₃, CH═CFCF₃, CH₂CH═CClCF₃, CH₂CH═CCl₂, CH₂CH═CBr₂, C≡CH, C≡CSiMe₃, C≡CSiEt₃, C≡CSiMe₂C(CH₃)₃, CaCCl, C≡CCF₃, C≡CCF₂H, C═CCF₂Cl, C═CCHFCl, C═CCF₂Me, C═CCF₂Et, C═CCHFEt, C≡CCF₂Br, C≡CCF(CF₃)₂, C═CCF₂CF₃, C≡CCHF(CF₃), C≡CCH₂F, C≡CCH(Me)F, C≡CMe, C═CCHMe₂, C≡CCH₂Me, Cs═CCH₂CHMe₂, C≡CCMe₃, C≡CCH₂CMe₃, C≡CCMe₂F, C≡CCH₂CF₃, C≡C(cyclopropyl), C≡C(cyclopentyl), C≡C(1-F-cyclopentyl), C≡CC(Me)═CH₂, C≡CCF═CF₂, C≡CCH₂SiMe₃, CH₂C≡CH, CF₂C≡CH or CHFC≡CH.

In one particular aspect R⁷ is even more preferably CH═CH₂, CH═CHSiMe₃, CH═CF₂, CH═CCl₂, CH═CBr₂, CF═CF₂, CCl═CH₂, CBr═CH₂, CF═CHF, CH═CHCF₃, CH═CClCF₃, C≡CH, C≡CSiMe₃, C≡CCl, C═CBr, C≡CCF₃, C═CMe, C≡CCMe₃, C≡CCHMe₂, C≡C(cycloC₃H₅), CH₂C≡CH, SiMe₃ or CH₂C≡CSiMe₃.

Yet more preferably R⁷ is CH═CF₂, CH═CCl₂, CH═CBr₂, CH═CFCl, CH═CFBr, CH═CHBr, CH═CHF, CH═CHCl, CCl═CH₂, CH═CHCF₃, CH═CFCF₂Cl, CH═CClCF₂Cl, CH═CBrCF₂Cl, CH═C(CF₃)₂, CH═CHC₂F₅, CH═CClCF₃, CH═CBrCF₃, CH═CFCF₃, C≡CH, C≡CSiMe₃, C≡CCl, C≡CCF₃, C≡CCF₂H, C≡CCHFCl, C≡CCHF(CF₃), C≡CCF₂Cl, C≡CCF₂Me, C≡CCF₂Br, C≡CCF₂CF₃, C═CCH₂F, C≡CCH(Me)F, C≡CMe, C≡CCHMe₂, C≡CCH₂CHMe₂, C≡CCMe₃, C≡CCCH₂CMe₃, C≡CCMe₂F, C≡CCH₂CF₃, C═C(cyclopropyl), C≡C(cyclopentyl), C≡C(1-F-cyclopentyl), CH₂C≡CH, CF₂C═CH, CHFC≡CH or C═CCH₂Me.

In one particular aspect R⁷ is yet more preferably CH═CHSiMe₃, CH═CF₂, CH═CCl₂, CH═CBr₂, CF═CF₂, CCl═CH₂, CBr═CH₂, CF═CHF, CH═CHCF₃, CH═CClCF₃, C≡CH, C≡CSiMe₃, C≡CCl, C≡CBr, C═CCF₃, C═CMe, C≡CCMe₃, C═CCHMe₂, C═C(cycloC₃H₅), CH₂C≡CH, SiMe₃ or CH₂C≡CSiMe₃.

Preferably nitrogen atoms in the Het ring are, independently, either unsubstituted or substituted by R^(y).

When R^(y) is a substituent on a nitrogen atom it is preferably C₁₋₃ alkyl, C₁₋₃ haloalkyl or methoxymethylene; more preferably C₁₋₂ alkyl, CF₃, CF₂Cl, CHF₂, CH₂F or methoxyrnethylene; even more preferably methyl, CHF₂ or methoxymethylene; yet more preferably methyl or methoxymethylene; and most preferably methyl.

Preferably carbon atoms in the Het ring which are not bonded to the atom substituted by CXNR¹ are, independently, either unsubstituted or substituted by R^(y).

When R^(y) is a substituent on a carbon atom which is not bonded to the atom substituted by CXNR¹ it is preferably halogen, C₁₋₃ alkyl, C₁₋₃ haloalkyl or methoxymethylene; more preferably chloro, methoxymethylene, CH₃, CHF₂ or CF₃; yet more preferably chloro, CH₃, CHF₂ or CF₃; and even more preferably CH₃ or CF₃. There may be one or two carbon atoms in the Het ring bonded to the atom substituted by CXNR¹; preferably such carbon atoms are, independently, either unsubstituted or substituted by R^(y).

When R^(y) is a substituent on a carbon atom bonded to the atom substituted by CXNR¹ it is preferably halogen, C₁₋₃ alkyl or C₁₋₃ haloalkyl; more preferably chloro, fluoro, bromo, C₁₋₂ alkyl, CF₃, CF₂Cl, CHF₂, CH₂F; and even more preferably chloro, fluoro, bromo, methyl, CF₃, CHF₂ or CH₂F.

More preferably, when there is only one carbon atom in the Het ring bonded to the atom substituted by CXNR¹ that carbon atom is substituted by R^(y).

More preferably, when there are two carbon atoms in the Het ring bonded to the atom substituted by CXNR¹ one such carbon atom is substituted by R^(y) and the other carbon atom is either unsubstituted or is substituted by fluoro, chloro or methyl.

Preferably m is 0.

Preferably n is 0.

Preferably X is O.

Compounds of formula (II):

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n are as defined above for a compound of formula (I), are also novel [except for the compound of formula (II) where R¹, R², R³, R⁴ and R⁵ are each hydrogen, n is 0 and R⁷is CH═CHCH₂CO₂H] and are useful as intermediates in the preparation of compounds of formula (I).

Therefore, in another aspect the present invention provides a compound of formula (II), where R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n are as defined above for a compound of formula (I) provided that when R¹, R², R³, R⁴ and R⁵ are each hydrogen and n is 0 then R⁷ is not CH═CHCH₂CO₂H.

The preferred values for R¹, R², R³,R⁴, R⁵, R⁶, R⁷ and n for a compound of formula (II) are as defined above for a compound of formula (I).

Many compounds of formula (E):

where R², R³, R⁴, R⁵, R⁶, R⁷ and n are as defined above for a compound of formula (I) and Hal is bromo, chloro or iodo, are also novel and are useful as intermediates in the preparation of compounds of formula (I).

Certain compounds of formula (III) are already known; Table 0 shows known compounds of formula (IIa) where Hal, R², R³, R⁴ and R⁷ are as defined in Table 0.

TABLE 0 Hal R² R³ R⁴ R⁷ Cl Cl H H C(CH₃)═CH—CH₂—OH Br H Me H C(CF₃)═CF₂ Br H Me Br C(CF₃)═CF₂ Cl H H H C≡CH Cl H H H CH═CH—CH₂—CH₂—OH Cl H H H C(CH₃)═CH—CH₂—OH Cl H H H C(CH₃)═CH—C(═O)—OC₂H₅ Cl H H H C(CH₃)═CH—CH(OH)CH₃ Cl H H H CH═CH—CH(OH)CH₃

Therefore, in a further aspect the present invention provides a compound of formula (M), where R², R³, R⁴, R⁵, R⁶, R⁷ and n are as defined above for a compound of formula (I) and Hal is bromo, chloro or iodo; provided that the compound is not a compound of formula (Ma) according to Table 0.

The preferred values for R², R³, R⁴, R⁵, R⁶, R⁷ and n for a compound of formula (III) are as defined above for a compound of formula (I).

Preferably Hal is bromo or chloro.

More preferably Hal is bromo.

The compounds of formulae (I), (II) and (III) may exist as different geometric or optical isomers or in different tautomeric forms. For each formula, this invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.

The compounds in Tables 1 to 13 below illustrate compounds of the invention. TABLE 1 Compound No. R¹ R⁷ R⁸ R⁹ R¹⁰ X 1.01 H C≡CH H Me CF₃ O 1.02 H C≡CH H Me CF₃ S 1.03 H C≡CH H Me CF₂H O 1.04 propargyl C≡CH H Me CF₃ O 1.05 H C≡CH F Me Me O 1.06 H C≡CH H CH₂OMe CF₃ O 1.07 allenyl C≡CH H Me CF₃ O 1.08 H C≡CSiMe₃ H Me CF₃ O 1.09 H C≡CSiMe₃ H Me CF₃ S 1.10 H C≡CSiMe₃ H Me CF₂H O 1.11 H C≡CSiMe₃ H Me Me O 1.12 H C≡CCl H Me CF₃ O 1.13 H C≡CCl H Me CF₂H O 1.14 H C≡CCl H Me Me O 1.15 H C≡CBr H Me CF₃ O 1.16 H C≡CBr H Me CF₂H O 1.17 H C≡CBr F Me Me O 1.18 H C≡CCF₃ H Me CF₃ O 1.19 H C≡CCF₃ H Me CF₂H O 1.20 H C≡CCF₃ F Me Me O 1.21 allenyl C≡CCF₃ H Me CF₃ O 1.22 H CH═CH₂ H Me CF₃ O 1.23 H CH═CH₂ H Me CF₃ S 1.24 H CH═CH₂ H Me CF₂H O 1.25 propargyl CH═CH₂ H Me CF₃ O 1.26 H CH═CH₂ F Me Me O 1.27 H CH═CH₂ H CH₂OMe CF₃ O 1.28 allenyl CH═CH₂ H Me CF₃ O 1.29 H CH═CF₂ H Me CF₃ O 1.30 H CH═CF₂ H Me CF₂H O 1.31 H CH═CF₂ F Me Me O 1.32 H CH═CCl₂ H Me CF₃ O 1.33 H CH═CCl₂ H Me CF₂H O 1.34 H CH═CCl₂ F Me Me O 1.35 H CH═CBr₂ H Me CF₃ O 1.36 H CH═CBr₂ H Me CF₂H O 1.37 H CH═CBr₂ F Me Me O 1.38 H CF═CF₂ H Me CF₃ O 1.39 H CF═CF₂ H Me CF₂H O 1.40 H CF═CF₂ F Me Me O 1.41 H CCl═CH₂ H Me CF₃ O 1.42 H CCl═CH₂ H Me CF₂H O 1.43 H CCl═CH₂ F Me Me O 1.44 H CBr═CH₂ H Me CF₃ O 1.45 H CBr═CH₂ H Me CF₂H O 1.46 H CBr═CH₂ F Me Me O 1.47 H CF═CHF H Me CF₃ O 1.48 H CF═CHF H Me CF₂H O 1.49 H CF═CHF F Me Me O 1.50 H CH═CHSiMe₃ H Me CF₃ O 1.51 H CH═CHSiMe₃ H Me CF₂H O 1.52 H CH═CHSiMe₃ F Me Me O 1.53 H CH═CHCF₃ H Me CF₃ O 1.54 H CH═CHCF₃ H Me CF₂H O 1.55 H CH═CHCF₃ F Me Me O 1.56 H CH═CClCF₃ H Me CF₃ O 1.57 H CH═CClCF₃ H Me CF₂H O 1.58 H CH═CClCF₃ F Me Me O 1.59 H CH₂C≡CH H Me CF₃ O 1.60 H CH₂C≡CH H Me CF₂H O 1.61 H CH₂C≡CH F Me Me O 1.62 H CH₂C≡CH H CH₂OMe CF₃ O 1.63 H CH₂C≡CSiMe₃ H Me CF₃ O 1.64 H CH₂C≡CSiMe₃ H Me CF₂H O 1.65 H CH₂C≡CSiMe₃ F Me Me O 1.66 H C≡CCMe₃ H Me CF₃ O 1.67 H C≡CCMe₃ H Me CF₂H O 1.68 H C≡CCMe₃ F Me Me O 1.69 H C≡CMe H Me CF₃ O 1.70 H C≡CMe H Me CF₂H O 1.71 H C≡CMe F Me Me O 1.72 COMe C≡CH H Me CF₃ O 1.73 H C≡CH H CF₂H CF₂H O 1.74 H C≡CH H CF₂H CF₃ O 1.75 H C≡CH H Me CH₂F O 1.76 H C≡CSiMe₃ H Me CH₂F O 1.77 H C≡C(cyclopropyl) H Me CF₃ O 1.78 H C≡C(cyclopropyl) H Me CHF₂ O 1.79 H SiMe₃ H Me CH₂F O 1.80 H SiMe₃ H Me CF₃ O 1.81 H SiMe₃ H Me CHF₂ O 1.82 H C≡CF H Me CF₃ O 1.83 H C≡CF H Me CF₂H O 1.84 H C≡CF F Me Me O 1.85 H C≡CCF₂Cl H Me CF₃ O 1.86 H C≡CCF₂Cl H Me CF₂H O 1.87 H C≡CCF₂Cl F Me Me O 1.88 H C≡CCF₂H H Me CF₃ O 1.89 H C≡CCF₂H H Me CF₂H O 1.90 H C≡CCF₂H F Me Me O 1.91 H C≡CCF₂Br H Me CF₃ O 1.92 H C≡CCF₂Br H Me CF₂H O 1.93 H C≡CCF₂Br F Me Me O 1.94 H C≡CCH₂F H Me CF₃ O 1.95 H C≡CCH₂F H Me CF₂H O 1.96 H C≡CCH₂F F Me Me O 1.97 H C≡CCH(Me)F H Me CF₃ O 1.98 H C≡CCH(Me)F H Me CF₂H O 1.99 H C≡CCH(Me)F F Me Me O 1.100 H C≡CC(Me)₂F H Me CF₃ O 1.101 H C≡CC(Me)₂F H Me CF₂H O 1.102 H C≡CC(Me)₂F F Me Me O 1.103 H C≡CCH₂C(Me)₃ H Me CF₃ O 1.104 H C≡CCH₂C(Me)₃ H Me CF₂H O 1.105 H C≡CCH₂C(Me)₃ F Me Me O 1.106 H C≡CCH(Me)₂ H Me CF₃ O 1.107 H C≡CCH(Me)₂ H Me CF₂H O 1.108 H C≡CCH(Me)₂ F Me Me O 1.109 H C≡CCH₂CH(Me)₂ H Me CF₃ O 1.110 H C≡CCH₂CH(Me)₂ H Me CF₂H O 1.111 H C≡CCH₂CH(Me)₂ F Me Me O 1.112 H CH₂C≡CCMe₃ H Me CF₃ O 1.113 H CH₂C≡CCMe₃ H Me CF₂H O 1.114 H CH₂C≡CCMe₃ F Me Me O 1.115 H CF₂C≡CCMe₃ H Me CF₃ O 1.116 H CF₂C≡CCMe₃ H Me CF₂H O 1.117 H CF₂C≡CCMe₃ F Me Me O 1.118 H CF₂C≡CMe H Me CF₃ O 1.119 H CF₂C≡CMe H Me CF₂H O 1.120 H CF₂C≡CMe F Me Me O 1.121 H CF₂C≡CH H Me CF₃ O 1.122 H CF₂C≡CH H Me CF₂H O 1.123 H CF₂C≡CH F Me Me O 1.124 H CMe₂C≡CH H Me CF₃ O 1.125 H CMe₂C≡CH H Me CF₂H O 1.126 H CMe₂C≡CH F Me Me O 1.127 H CHFC≡CH H Me CF₃ O 1.128 H CHFC≡CH H Me CF₂H O 1.129 H CHFC≡CH F Me Me O 1.130 H CHMeC≡CH H Me CF₃ O 1.131 H CHMeC≡CH H Me CF₂H O 1.132 H CHMeC≡CH F Me Me O 1.133 H CH(CF₃)C≡CH H Me CF₃ O 1.134 H CH(CF₃)C≡CH H Me CF₂H O 1.135 H CH(CF₃)C≡CH F Me Me O 1.136 H C≡C (1-F-cyclopentyl) H Me CF₃ O 1.137 H C≡C (1-F-cyclopentyl) H Me CHF₂ O 1.138 H C≡CCH₂OMe H Me CF₃ O 1.139 H C≡CCH₂OMe H Me CF₂H O 1.140 H C≡CCH₂OMe F Me Me O 1.141 H C≡CCMe₂OMe H Me CF₃ O 1.142 H C≡CCMe₂OMe H Me CF₂H O 1.143 H C≡CCMe₂OMe F Me Me O 1.144 H C≡CCMe₂OCOMe H Me CF₃ O 1.145 H C≡CCMe₂OCOMe H Me CF₂H O 1.146 H C≡CCF₂Me H Me CF₃ O 1.147 H C≡CCF₂Me H Me CF₂H O 1.148 H C≡CCF₂Me F Me Me O 1.149 H C≡CC(Me)═CH₂ H Me CF₃ O 1.150 H C≡CC(Me)═CH₂ H Me CF₂H O 1.151 H CH═CFCl H Me CF₃ O 1.152 H CH═CFCl H Me CF₂H O 1.153 H CH═CFCl F Me Me O 1.154 H CH═CFBr H Me CF₃ O 1.155 H CH═CFBr H Me CF₂H O 1.156 H CH═CFBr F Me Me O 1.157 H CH═CHBr H Me CF₃ O 1.158 H CH═CHBr H Me CF₂H O 1.159 H CH═CHBr F Me Me O 1.160 H CH═CHF H Me CF₃ O 1.161 H CH═CHF H Me CF₂H O 1.162 H CH═CHF F Me Me O 1.163 H CMe═CHCF₃ H Me CF₃ O 1.164 H CMe═CHCF₃ H Me CF₂H O 1.165 H CMe═CHCF₃ F Me Me O 1.166 H CH═CFCF₃ H Me CF₃ O 1.167 H CH═CFCF₃ H Me CF₂H O 1.168 H CH═CFCF₃ F Me Me O 1.169 H CH═CBrCF₃ H Me CF₃ O 1.170 H CH═CBrCF₃ H Me CF₂H O 1.171 H CH═CBrCF₃ F Me Me O 1.172 H CH═CHC₂F₅ H Me CF₃ O 1.173 H CH═CHC₂F₅ H Me CF₂H O 1.174 H CH═CHC₂F₅ F Me Me O 1.175 H CH═CHCl H Me CF₃ O 1.176 H CH═CHCl H Me CF₂H O 1.177 H CH═CHCl F Me Me O 1.178 H CH═C(CF₃)₂ H Me CF₃ O 1.179 H CH═C(CF₃)₂ H Me CF₂H O 1.180 H CH═C(CF₃)₂ F Me Me O 1.181 H CMe═CFCl H Me CF₃ O 1.182 H CMe═CFCl H Me CF₂H O 1.183 H CMe═CFCl F Me Me O 1.184 H CMe═CFBr H Me CF₃ O 1.185 H CMe═CFBr H Me CF₂H O 1.186 H CMe═CFBr F Me Me O 1.187 H CMe═CF₂ H Me CF₃ O 1.188 H CMe═CF₂ H Me CF₂H O 1.189 H CMe═CF₂ F Me Me O 1.190 H CMe═CCl₂ H Me CF₃ O 1.191 H CMe═CCl₂ H Me CF₂H O 1.192 H CMe═CCl₂ F Me Me O 1.193 H CMe═CBr₂ H Me CF₃ O 1.194 H CMe═CBr₂ H Me CF₂H O 1.195 H CMe═CBr₂ F Me Me O 1.196 H CMe═CFCF₃ H Me CF₃ O 1.197 H CMe═CFCF₃ H Me CF₂H O 1.198 H CMe═CFCF₃ F Me Me O 1.199 H CMe═CClCF₃ H Me CF₃ O 1.200 H CMe═CClCF₃ H Me CF₂H O 1.201 H CMe═CClCF₃ F Me Me O 1.202 H CCF₃═CF₂ H Me CF₃ O 1.203 H CCF₃═CF₂ H Me CF₂H O 1.204 H CCF₃═CF₂ F Me Me O 1.205 H CCF₃═CCl₂ H Me CF₃ O 1.206 H CCF₃═CCl₂ H Me CF₂H O 1.207 H CCF₃═CCl₂ F Me Me O 1.208 H CCF₃═CBr₂ H Me CF₃ O 1.209 H CCF₃═CBr₂ H Me CF₂H O 1.210 H CCF₃═CBr₂ F Me Me O 1.211 H CCF₃═CH₂ H Me CF₃ O 1.212 H CCF₃═CH₂ H Me CF₂H O 1.213 H CCF₃═CH₂ F Me Me O 1.214 H CCF₃═CFBr H Me CF₃ O 1.215 H CCF₃═CFBr H Me CF₂H O 1.216 H CCF₃═CFBr F Me Me O 1.217 H CCF₃═CHF H Me CF₃ O 1.218 H CCF₃═CHF H Me CF₂H O 1.219 H CCF₃═CHF F Me Me O 1.220 H CCF₃═CFCl H Me CF₃ O 1.221 H CCF₃═CFCl H Me CF₂H O 1.222 H CCF₃═CFCl F Me Me O 1.223 H CCF₃═CHCl H Me CF₃ O 1.224 H CCF₃═CHCl H Me CF₂H O 1.225 H CCF₃═CHCl F Me Me O 1.226 H CH═CFCF₂Cl H Me CF₃ O 1.227 H CH═CFCF₂Cl H Me CF₂H O 1.228 H CH═CFCF₂Cl F Me Me O 1.229 H CH═CClCF₂Cl H Me CF₃ O 1.230 H CH═CClCF₂Cl H Me CF₂H O 1.231 H CH═CClCF₂Cl F Me Me O 1.232 H CH₂CF═CF₂ H Me CF₃ O 1.233 H CH₂CF═CF₂ H Me CF₂H O 1.234 H CH₂CF═CF₂ F Me Me O 1.235 H CF═CFBr H Me CF₃ O 1.236 H CF═CFBr H Me CF₂H O 1.237 H CF═CFBr F Me Me O 1.238 H CH₂CH═CF₂ H Me CF₃ O 1.239 H CH₂CH═CF₂ H Me CF₂H O 1.240 H CH₂CH═CF₂ F Me Me O 1.241 H CH₂CH═CCl₂ H Me CF₃ O 1.242 H CH₂CH═CCl₂ H Me CF₂H O 1.243 H CH₂CH═CCl₂ F Me Me O 1.244 H CH₂CH═CBr₂ H Me CF₃ O 1.245 H CH₂CH═CBr₂ H Me CF₂H O 1.246 H CH₂CH═CBr₂ F Me Me O 1.247 H CCl═CF₂ H Me CF₃ O 1.248 H CCl═CF₂ H Me CF₂H O 1.249 H CCl═CF₂ F Me Me O 1.250 H C≡CCMe₂OH H Me CF₃ O 1.251 H C≡CCMe₂OH H Me CF₂H O 1.252 H C≡CSi(Me₂)CMe₃ H Me CF₃ O 1.253 H C≡CSi(Me₂)CMe₃ H Me CF₂H O 1.254 H C≡CCH₂SiMe₃ H Me CF₃ O 1.255 H C≡CCH₂SiMe₃ H Me CF₂H O 1.256 H C≡CCH₂SiMe₃ F Me Me O 1.257 H C≡CCMe₃ H CF₂H CF₃ O 1.258 H C≡CCH₂CF₃ H Me CF₃ O 1.259 H C≡CCH₂CF₃ H Me CF₂H O 1.260 H C≡CCH₂CF₃ F Me Me O 1.261 H C≡CCMe₃ H CF₂H CF₂H O 1.262 H C≡CCH₂CH₃ H Me CF₃ O 1.263 H C≡CCH₂CH₃ H Me CF₂H O 1.264 H C≡CCH₂CH₃ F Me Me O 1.265 H C≡CCF═CF₂ H Me CF₃ O 1.266 H C≡CCF═CF₂ H Me CF₂H O 1.267 H C≡CCHFCl H Me CF₃ O 1.268 H C≡CCHFCl H Me CF₂H O 1.269 H C≡CCHFCl F Me Me O 1.270 H CH═CFC₂F₅ H Me CF₃ O 1.271 H CH═CFC₂F₅ H Me CF₂H O 1.272 H CH═CFC₂F₅ F Me Me O 1.273 H C≡CCF₂CH₂CH₃ H Me CF₃ O 1.274 H C≡CCF₂CH₂CH₃ H Me CF₂H O 1.275 H C≡CCF₂CH₂CH₃ F Me Me O 1.276 H C≡CCHFCH₂CH₃ H Me CF₃ O 1.277 H C≡CCHFCH₂CH₃ H Me CF₂H O 1.278 H C≡CCHFCH₂CH₃ F Me Me O 1.279 H C≡CCF(CF₃)₂ H Me CF₃ O 1.280 H C≡CCF(CF₃)₂ H Me CF₂H O 1.281 H C≡CCF(CF₃)₂ F Me Me O 1.282 H CH═CClC₂F₅ H Me CF₃ O 1.283 H CH═CClC₂F₅ H Me CF₂H O 1.284 H CH═CClC₂F₅ F Me Me O 1.285 H C≡CC₂F₅ H Me CF₃ O 1.286 H C≡CC₂F₅ H Me CF₂H O 1.287 H C≡CC₂F₅ F Me Me O

Table 1 provides 287 compounds of formula (Ia):

wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IA):

wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaB) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaC) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaD) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaE) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaF) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaG) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined as Table 1.

Table 1 provides 287 compounds of fornula (IaH) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaI) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

Table 1 provides 287 compounds of formula (IaJ) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 1.

TABLE 2 Compound No. R¹ R⁷ R⁸ R⁹ R¹⁰ X 2.01 H C≡CH H Me CF₃ O 2.02 H C≡CH H Me CF₃ S 2.03 H C≡CH H Me CF₂H O 2.04 propargyl C≡CH H Me CF₃ O 2.05 H C≡CH F Me Me O 2.06 H C≡CH H CH₂OMe CF₃ O 2.07 allenyl C≡CH H Me CF₃ O 2.08 H C≡CSiMe₃ H Me CF₃ O 2.09 H C≡CSiMe₃ H Me CF₃ S 2.10 H C≡CSiMe₃ H Me CF₂H O 2.11 H C≡CSiMe₃ F Me Me O 2.12 H C≡CCl H Me CF₃ O 2.13 H C≡CCl H Me CF₂H O 2.14 H C≡CCl F Me Me O 2.15 H C≡CBr H Me CF₃ O 2.16 H C≡CBr H Me CF₂H O 2.17 H C≡CBr F Me Me O 2.18 H C≡CCF₃ H Me CF₃ O 2.19 H C≡CCF₃ H Me CF₂H O 2.20 H C≡CCF₃ F Me Me O 2.21 allenyl C≡CCF₃ H Me CF₃ O 2.22 H CH═CH₂ H Me CF₃ O 2.23 H CH═CH₂ H Me CF₃ S 2.24 H CH═CH₂ H Me CF₂H O 2.25 propargyl CH═CH₂ H Me CF₃ O 2.26 H CH═CH₂ F Me Me O 2.27 H CH═CH₂ H CH₂OMe CF₃ O 2.28 allenyl CH═CH₂ H Me CF₃ O 2.29 H CH═CF₂ H Me CF₃ O 2.30 H CH═CF₂ H Me CF₂H O 2.31 H CH═CF₂ F Me Me O 2.32 H CH═CCl₂ H Me CF₃ O 2.33 H CH═CCl₂ H Me CF₂H O 2.34 H CH═CCl₂ F Me Me O 2.35 H CH═CBr₂ H Me CF₃ O 2.36 H CH═CBr₂ H Me CF₂H O 2.37 H CH═CBr₂ F Me Me O 2.38 H CF═CF₂ H Me CF₃ O 2.39 H CF═CF₂ H Me CF₂H O 2.40 H CF═CF₂ F Me Me O 2.41 H CCl═CH₂ H Me CF₃ O 2.42 H CCl═CH₂ H Me CF₂H O 2.43 H CCl═CH₂ F Me Me O 2.44 H CBr═CH₂ H Me CF₃ O 2.45 H CBr═CH₂ H Me CF₂H O 2.46 H CBr═CH₂ F Me Me O 2.47 H CF═CHF H Me CF₃ O 2.48 H CF═CHF H Me CF₂H O 2.49 H CF═CHF F Me Me O 2.50 H CH═CHSiMe₃ H Me CF₃ O 2.51 H CH═CHSiMe₃ H Me CF₂H O 2.52 H CH═CHSiMe₃ F Me Me O 2.53 H CH═CHCF₃ H Me CF₃ O 2.54 H CH═CHCF₃ H Me CF₂H O 2.55 H CH═CHCF₃ F Me Me O 2.56 H CH═CClCF₃ H Me CF₃ O 2.57 H CH═CClCF₃ H Me CF₂H O 2.58 H CH═CClCF₃ F Me Me O 2.59 H CH₂C≡CH H Me CF₃ O 2.60 H CH₂C≡CH H Me CF₂H O 2.61 H CH₂C≡CH F Me Me O 2.62 H CH₂C≡CH H CH₂OMe CF₃ O 2.63 H CH₂C≡CSiMe₃ H Me CF₃ O 2.64 H CH₂C≡CSiMe₃ H Me CF₂H O 2.65 H CH₂C≡CSiMe₃ F Me Me O 2.66 H C≡CCMe₃ H Me CF₃ O 2.67 H C≡CCMe₃ H Me CF₂H O 2.68 H C≡CCMe₃ F Me Me O 2.69 H C≡CMe H Me CF₃ O 2.70 H C≡CMe H Me CF₂H O 2.71 H C≡CMe F Me Me O 2.72 COMe C≡CH H Me CF₃ O 2.73 H C≡CH H CF₂H CF₂H O 2.74 H C≡CH H CF₂H CF₃ O 2.75 H C≡CH H Me CH₂F O 2.76 H C≡CSiMe₃ H Me CH₂F O 2.77 H C≡C(cyclopropyl) H Me CF₃ O 2.78 H C≡C(cyclopropyl) H Me CHF₂ O 2.79 H SiMe₃ H Me CH₂F O 2.80 H SiMe₃ H Me CF₃ O 2.81 H SiMe₃ H Me CHF₂ O 2.82 H C≡CF H Me CF₃ O 2.83 H C≡CF H Me CF₂H O 2.84 H C≡CF F Me Me O 2.85 H C≡CCF₂Cl H Me CF₃ O 2.86 H C≡CCF₂Cl H Me CF₂H O 2.87 H C≡CCF₂Cl F Me Me O 2.88 H C≡CCF₂H H Me CF₃ O 2.89 H C≡CCF₂H H Me CF₂H O 2.90 H C≡CCF₂H F Me Me O 2.91 H C≡CCF₂Br H Me CF₃ O 2.92 H C≡CCF₂Br H Me CF₂H O 2.93 H C≡CCF₂Br F Me Me O 2.94 H C≡CCH₂F H Me CF₃ O 2.95 H C≡CCH₂F H Me CF₂H O 2.96 H C≡CCH₂F F Me Me O 2.97 H C≡CCH(Me)F H Me CF₃ O 2.98 H C≡CCH(Me)F H Me CF₂H O 2.99 H C≡CCH(Me)F F Me Me O 2.100 H C≡CC(Me)₂F H Me CF₃ O 2.101 H C≡CC(Me)₂F H Me CF₂H O 2.102 H C≡CC(Me)₂F F Me Me O 2.103 H C≡CCH₂C(Me)₃ H Me CF₃ O 2.104 H C≡CCH₂C(Me)₃ H Me CF₂H O 2.105 H C≡CCH₂C(Me)₃ F Me Me O 2.106 H C≡CCH(Me)₂ H Me CF₂H O 2.107 H C≡CCH(Me)₂ H Me CF₂H O 2.108 H C≡CCH(Me)₂ F Me Me O 2.109 H C≡CCH₂CH(Me)₂ H Me CF₂H O 2.110 H C≡CCH₂CH(Me)₂ H Me CF₂H O 2.111 H C≡CCH₂CH(Me)₂ F Me Me O 2.112 H CH₂C≡CCMe₃ H Me CF₃ O 2.113 H CH₂C≡CCMe₃ H Me CF₂H O 2.114 H CH₂C≡CCMe₃ F Me Me O 2.115 H CF₂C≡CCMe₃ H Me CF₃ O 2.116 H CF₂C≡CCMe₃ H Me CF₂H O 2.117 H CF₂C≡CCMe₃ F Me Me O 2.118 H CF₂C≡CMe H Me CF₃ O 2.119 H CF₂C≡CMe H Me CF₂H O 2.120 H CF₂C≡CCMe F Me Me O 2.121 H CF₂C≡CH H Me CF₃ O 2.122 H CF₂C≡CH H Me CF₂H O 2.123 H CF₂C≡CH F Me Me O 2.124 H CMe₂C≡CH H Me CF₃ O 2.125 H CMe₂C≡CH H Me CF₂H O 2.126 H CMe₂C≡CH F Me Me O 2.127 H CHFC≡CH H Me CF₃ O 2.128 H CHFC≡CH H Me CF₂H O 2.129 H CHFC≡CH F Me Me O 2.130 H CHMeC≡CH H Me CF₃ O 2.131 H CHMeC≡CH H Me CF₂H O 2.132 H CHMeC≡CH F Me Me O 2.133 H CH(CF₃)C≡CH H Me CF₃ O 2.134 H CH(CF₃)C≡CH H Me CF₂H O 2.135 H CH(CF₃)C≡CH F Me Me O 2.136 H C≡C(1-F-cyclopentyl) H Me CF₃ O 2.137 H C≡C(1-F-cyclopentyl) H Me CHF₂ O 2.138 H C≡CCH₂OMe H Me CF₃ O 2.139 H C≡CCH₂OMe H Me CF₂H O 2.140 H C≡CCH₂OMe F Me Me O 2.141 H C≡CCMe₂OMe H Me CF₃ O 2.142 H C≡CCMe₂OMe H Me CF₂H O 2.143 H C≡CCMe₂OMe F Me Me O 2.144 H C≡CCMe₂OCOMe H Me CF₃ O 2.145 H C≡CCMe₂OCOMe H Me CF₂H O 2.146 H C≡CCF₂Me H Me CF₃ O 2.147 H C≡CCF₂Me H Me CF₂H O 2.148 H C≡CCF₂Me F Me Me O 2.149 H C≡CC(Me)═CH₂ H Me CF₃ O 2.150 H C≡CC(Me)═CH₂ H Me CF₂H O 2.151 H CH═CFCl H Me CF₃ O 2.152 H CH═CFCl H Me CF₂H O 2.153 H CH═CFCl F Me Me O 2.154 H CH═CFBr H Me CF₃ O 2.155 H CH═CFBr H Me CF₂H O 2.156 H CH═CFBr F Me Me O 2.157 H CH═CHBr H Me CF₃ O 2.158 H CH═CHBr H Me CF₂H O 2.159 H CH═CHBr F Me Me O 2.160 H CH═CHF H Me CF₃ O 2.161 H CH═CHF H Me CF₂H O 2.162 H CH═CHF F Me Me O 2.163 H CMe═CHCF₃ H Me CF₃ O 2.164 H CMe═CHCF₃ H Me CF₂H O 2.165 H CMe═CHCF₃ F Me Me O 2.166 H CH═CFCF₃ H Me CF₃ O 2.167 H CH═CFCF₃ H Me CF₂H O 2.168 H CH═CFCF₃ F Me Me O 2.169 H CH═CBrCF₃ H Me CF₃ O 2.170 H CH═CBrCF₃ H Me CF₂H O 2.171 H CH═CBrCF₃ F Me Me O 2.172 H CH═CHC₂F₅ H Me CF₃ O 2.173 H CH═CHC₂F₅ H Me CF₂H O 2.174 H CH═CHC₂F₅ F Me Me O 2.175 H CH═CHCl H Me CF₃ O 2.176 H CH═CHCl H Me CF₂H O 2.177 H CH═CHCl F Me Me O 2.178 H CH═C(CF₃)₂ H Me CF₃ O 2.179 H CH═C(CF₃)₂ H Me CF₂H O 2.180 H CH═C(CF₃)₂ F Me Me O 2.181 H CMe═CFCl H Me CF₃ O 2.182 H CMe═CFCl H Me CF₂H O 2.183 H CMe═CFCl F Me Me O 2.184 H CMe═CFBr H Me CF₃ O 2.185 H CMe═CFBr H Me CF₂H O 2.186 H CMe═CFBr F Me Me O 2.187 H CMe═CF₂ H Me CF₃ O 2.188 H CMe═CF₂ H Me CF₂H O 2.189 H CMe═CF₂ F Me Me O 2.190 H CMe═CCl₂ H Me CF₃ O 2.191 H CMe═CCl₂ H Me CF₂H O 2.192 H CMe═CCl₂ F Me Me O 2.193 H CMe═CBr₂ H Me CF₃ O 2.194 H CMe═CBr₂ H Me CF₂H O 2.195 H CMe═CBr₂ F Me Me O 2.196 H CMe═CFCF₃ H Me CF₃ O 2.197 H CMe═CFCF₃ H Me CF₂H O 2.198 H CMe═CFCF₃ F Me Me O 2.199 H CMe═CClCF₃ H Me CF₃ O 2.200 H CMe═CClCF₃ H Me CF₂H O 2.201 H CMe═CClCF₃ F Me Me O 2.202 H CCF₃═CF₂ H Me CF₃ O 2.203 H CCF₃═CF₂ H Me CF₂H O 2.204 H CCF₃═CF₂ F Me Me O 2.205 H CCF₃═CCl₂ H Me CF₃ O 2.206 H CCF₃═CCl₂ H Me CF₂H O 2.207 H CCF₃═CCl₂ F Me Me O 2.208 H CCF₃═CBr₂ H Me CF₃ O 2.209 H CCF₃═CBr₂ H Me CF₂H O 2.210 H CCF₃═CBr₂ F Me Me O 2.211 H CCF₃═CH₂ H Me CF₃ O 2.212 H CCF₃═CH₂ H Me CF₂H O 2.213 H CCF₃═CH₂ F Me Me O 2.214 H CCF₃═CFBr H Me CF₃ O 2.215 H CCF₃═CFBr H Me CF₂H O 2.216 H CCF₃═CFBr F Me Me O 2.217 H CCF₃═CHF H Me CF₃ O 2.218 H CCF₃═CHF H Me CF₂H O 2.219 H CCF₃═CHF F Me Me O 2.220 H CCF₃═CFCl H Me CF₃ O 2.221 H CCF₃═CFCl H Me CF₂H O 2.222 H CCF₃═CFCl F Me Me O 2.223 H CCF₃═CHCl H Me CF₃ O 2.224 H CCF₃═CHCl H Me CF₂H O 2.225 H CCF₃═CHCl F Me Me O 2.226 H CH═CFCF₂Cl H Me CF₃ O 2.227 H CH═CFCF₂Cl H Me CF₂H O 2.228 H CH═CFCF₂Cl F Me Me O 2.229 H CH═CClCF₂Cl H Me CF₃ O 2.230 H CH═CClCF₂Cl H Me CF₂H O 2.231 H CH═CClCF₂Cl F Me Me O 2.232 H CH₂CF═CF₂ H Me CF₃ O 2.233 H CH₂CF═CF₂ H Me CF₂H O 2.234 H CH₂CF═CF₂ F Me Me O 2.235 H CF═CFBr H Me CF₃ O 2.236 H CF═CFBr H Me CF₂H O 2.237 H CF═CFBr F Me Me O 2.238 H CH₂CH═CF₂ H Me CF₃ O 2.239 H CH₂CH═CF₂ H Me CF₂H O 2.240 H CH₂CH═CF₂ F Me Me O 2.241 H CH₂CH═CCl₂ H Me CF₃ O 2.242 H CH₂CH═CCl₂ H Me CF₂H O 2.243 H CH₂CH═CCl₂ F Me Me O 2.244 H CH₂CH═CBr₂ H Me CF₃ O 2.245 H CH₂CH═CBr₂ H Me CF₂H O 2.246 H CH₂CH═CBr₂ F Me Me O 2.247 H CCl═CF₂ H Me CF₃ O 2.248 H CCl═CF₂ H Me CF₂H O 2.249 H CCl═CF₂ F Me Me O

Table 2 provides 249 compounds of formula (Ib) wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and X are as defined in Table 2.

TABLE 3 Compound No. R¹ R⁷ R⁹ R¹⁰ X 3.01 H C≡CH Me CF₃ O 3.02 H C≡CH Me CF₃ S 3.03 H C≡CH Me CF₂H O 3.04 propargyl C≡CH Me CF₃ O 3.05 H C≡CH Me Me O 3.06 H C≡CH CH₂OMe CF₃ O 3.07 allenyl C≡CH Me CF₃ O 3.08 H C≡CSiMe₃ Me CF₃ O 3.09 H C≡CSiMe₃ Me CF₃ S 3.10 H C≡CSiMe₃ Me CF₂H O 3.11 H C≡CSiMe₃ Me Me O 3.12 H C≡CCl Me CF₃ O 3.13 H C≡CCl Me CF₂H O 3.14 H C≡CCl Me Me O 3.15 H C≡CBr Me CF₃ O 3.16 H C≡CBr Me CF₂H O 3.17 H C≡CBr Me Me O 3.18 H C≡CCF₃ Me CF₃ O 3.19 H C≡CCF₃ Me CF₂H O 3.20 H C≡CCF₃ Me Me O 3.21 allenyl C≡CCF₃ Me CF₃ O 3.22 H CH═CH₂ Me CF₃ O 3.23 H CH═CH₂ Me CF₃ S 3.24 H CH═CH₂ Me CF₂H O 3.25 propargyl CH═CH₂ Me CF₃ O 3.26 H CH═CH₂ Me Me O 3.27 H CH═CH₂ CH₂OMe CF₃ O 3.28 allenyl CH═CH₂ Me CF₃ O 3.29 H CH═CF₂ Me CF₃ O 3.30 H CH═CF₂ Me CF₂H O 3.31 H CH═CF₂ Me Me O 3.32 H CH═CCl₂ Me CF₃ O 3.33 H CH═CCl₂ Me CF₂H O 3.34 H CH═CCl₂ Me Me O 3.35 H CH═CBr₂ Me CF₃ O 3.36 H CH═CBr₂ Me CF₂H O 3.37 H CH═CBr₂ Me Me O 3.38 H CF═CF₂ Me CF₃ O 3.39 H CF═CF₂ Me CF₂H O 3.40 H CF═CF₂ Me Me O 3.41 H CCl═CH₂ Me CF₃ O 3.42 H CCl═CH₂ Me CF₂H O 3.43 H CCl═CH₂ Me Me O 3.44 H CBr═CH₂ Me CF₃ O 3.45 H CBr═CH₂ Me CF₂H O 3.46 H CBr═CH₂ Me Me O 3.47 H CF═CHF Me CF₃ O 3.48 H CF═CHF Me CF₂H O 3.49 H CF═CHF Me Me O 3.50 H CH═CHSiMe₃ Me CF₃ O 3.51 H CH═CHSiMe₃ Me CF₂H O 3.52 H CH═CHSiMe₃ Me Me O 3.53 H CH═CHCF₃ Me CF₃ O 3.54 H CH═CHCF₃ Me CF₂H O 3.55 H CH═CHCF₃ Me Me O 3.56 H CH═CClCF₃ Me CF₃ O 3.57 H CH═CClCF₃ Me CF₂H O 3.58 H CH═CClCF₃ Me Me O 3.59 H CH₂C≡CH Me CF₃ O 3.60 H CH₂C≡CH Me CF₂H O 3.61 H CH₂C≡CH Me Me O 3.62 H CH₂C≡CH CH₂OMe CF₃ O 3.63 H CH₂C≡CSiMe₃ Me CF₃ O 3.64 H CH₂C≡CSiMe₃ Me CF₂H O 3.65 H CH₂C≡CSiMe₃ Me Me O 3.66 H C≡CCMe₃ Me CF₃ O 3.67 H C≡CCMe₃ Me CF₂H O 3.68 H C≡CCMe₃ Me Me O 3.69 H C≡CMe Me CF₃ O 3.70 H C≡CMe Me CF₂H O 3.71 H C≡CMe Me Me O 3.72 COMe C≡CH Me CF₃ O 3.73 H C≡CH CF₂H CF₂H O 3.74 H C≡CH CF₂H CF₃ O 3.75 H C≡CH Me CH₂F O 3.76 H C≡CSiMe₃ Me CH₂F O 3.77 H C≡C(cyclopropyl) Me CF₃ O 3.78 H C≡C(cyclopropyl) Me CHF₂ O 3.79 H SiMe₃ Me CH₂F O 3.80 H SiMe₃ Me CF₃ O 3.81 H SiMe₃ Me CHF₂ O 3.82 H C≡CF Me CF₃ O 3.83 H C≡CF Me CF₂H O 3.84 H C≡CF Me Me O 3.85 H C≡CCF₂Cl Me CF₃ O 3.86 H C≡CCF₂Cl Me CF₂H O 3.87 H C≡CCF₂Cl Me Me O 3.88 H C≡CCF₂H Me CF₃ O 3.89 H C≡CCF₂H Me CF₂H O 3.90 H C≡CCF₂H Me Me O 3.91 H C≡CCF₂Br Me CF₃ O 3.92 H C≡CCF₂Br Me CF₂H O 3.93 H C≡CCF₂Br Me Me O 3.94 H C≡CCH₂F Me CF₃ O 3.95 H C≡CCH₂F Me CF₂H O 3.96 H C≡CCH₂F Me Me O 3.97 H C≡CCH(Me)F Me CF₃ O 3.98 H C≡CCH(Me)F Me CF₂H O 3.99 H C≡CCH(Me)F Me Me O 3.100 H C≡CC(Me)₂F Me CF₃ O 3.101 H C≡CC(Me)₂F Me CF₂H O 3.102 H C≡CC(Me)₂F Me Me O 3.103 H C≡CCH₂C(Me)₃ Me CF₃ O 3.104 H C≡CCH₂C(Me)₃ Me CF₂H O 3.105 H C≡CCH₂C(Me)₃ Me Me O 3.106 H C≡CCH(Me)₂ Me CF₃ O 3.107 H C≡CCH(Me)₂ Me CF₂H O 3.108 H C≡CCH(Me)₂ Me Me O 3.109 H C≡CCH₂CH(Me)₂ Me CF₃ O 3.110 H C≡CCH₂CH(Me)₂ Me CF₂H O 3.111 H C≡CCH₂CH(Me)₂ Me Me O 3.112 H CH₂C≡CCMe₃ Me CF₃ O 3.113 H CH₂C≡CCMe₃ Me CF₂H O 3.114 H CH₂C≡CCMe₃ Me Me O 3.115 H CF₂C≡CCMe₃ Me CF₃ O 3.116 H CF₂C≡CCMe₃ Me CF₂H O 3.117 H CF₂C≡CCMe₃ Me Me O 3.118 H CF₂C≡CMe Me CF₃ O 3.119 H CF₂C≡CMe Me CF₂H O 3.120 H CF₂C≡CCMe Me Me O 3.121 H CF₂C≡CH Me CF₃ O 3.122 H CF₂C≡CH Me CF₂H O 3.123 H CF₂C≡CH Me Me O 3.124 H CMe₂C≡CH Me CF₃ O 2.125 H CMe₂C≡CH Me CF₂H O 3.126 H CMe₂C≡CH Me Me O 3.127 H CHFC≡CH Me CF₃ O 3.128 H CHFC≡CH Me CF₂H O 3.129 H CHFC≡CH Me Me O 3.130 H CHMeC≡CH Me CF₃ O 3.131 H CHMeC≡CH Me CF₂H O 3.132 H CHMeC≡CH Me Me O 3.133 H CH(CF₃)C≡CH Me CF₃ O 3.134 H CH(CF₃)C≡CH Me CF₂H O 3.135 H CH(CF₃)C≡CH Me Me O 3.136 H C≡C(1-F-cyclopentyl) Me CF₃ O 3.137 H C≡C(1-F-cyclopentyl) Me CHF₂ O 3.138 H C≡CCH₂OMe Me CF₃ O 3.139 H C≡CCH₂OMe Me CF₂H O 3.140 H C≡CCH₂OMe Me Me O 3.141 H C≡CCMe₂OMe Me CF₃ O 3.142 H C≡CCMe₂OMe Me CF₂H O 3.143 H C≡CCMe₂OMe Me Me O 3.144 H C≡CCMe₂OCOMe Me CF₃ O 3.145 H C≡CCMe₂OCOMe Me CF₂H O 3.146 H C≡CCF₂Me Me CF₃ O 3.147 H C≡CCF₂Me Me CF₂H O 3.148 H C≡CCF₂Me Me Me O 3.149 H C≡CC(Me)═CH₂ Me CF₃ O 3.150 H C≡CC(Me)═CH₂ Me CF₂H O 3.151 H CH═CFCl Me CF₃ O 3.152 H CH═CFCl Me CF₂H O 3.153 H CH═CFCl Me Me O 3.154 H CH═CFBr Me CF₃ O 3.155 H CH═CFBr Me CF₂H O 3.156 H CH═CFBr Me Me O 3.157 H CH═CHBr Me CF₃ O 3.158 H CH═CHBr Me CF₂H O 3.159 H CH═CHBr Me Me O 3.160 H CH═CHF Me CF₃ O 3.161 H CH═CHF Me CF₂H O 3.162 H CH═CHF Me Me O 3.163 H CMe═CHCF₃ Me CF₃ O 3.164 H CMe═CHCF₃ Me CF₂H O 3.165 H CMe═CHCF₃ Me Me O 3.166 H CH═CFCF₃ Me CF₃ O 3.167 H CH═CFCF₃ Me CF₂H O 3.168 H CH═CFCF₃ Me Me O 3.169 H CH═CBrCF₃ Me CF₃ O 3.170 H CH═CBrCF₃ Me CF₂H O 3.171 H CH═CBrCF₃ Me Me O 3.172 H CH═CHC₂F₅ Me CF₃ O 3.173 H CH═CHC₂F₅ Me CF₂H O 3.174 H CH═CHC₂F₅ Me Me O 3.175 H CH═CHCl Me CF₃ O 3.176 H CH═CHCl Me CF₂H O 3.177 H CH═CHCl Me Me O 3.178 H CH═C(CF₃)₂ Me CF₃ O 3.179 H CH═C(CF₃)₂ Me CF₂H O 3.180 H CH═C(CF₃)₂ Me Me O 3.181 H CMe═CFCl Me CF₃ O 3.182 H CMe═CFCl Me CF₂H O 3.183 H CMe═CFCl Me Me O 3.184 H CMe═CFBr Me CF₃ O 3.185 H CMe═CFBr Me CF₂H O 3.186 H CMe═CFBr Me Me O 3.187 H CMe═CF₂ Me CF₃ O 3.188 H CMe═CF₂ Me CF₂H O 3.189 H CMe═CF₂ Me Me O 3.190 H CMe═CCl₂ Me CF₃ O 3.191 H CMe═CCl₂ Me CF₂H O 3.192 H CMe═CCl₂ Me Me O 3.193 H CMe═CBr₂ Me CF₃ O 3.194 H CMe═CBr₂ Me CF₂H O 3.195 H CMe═CBr₂ Me Me O 3.196 H CMe═CFCF₃ Me CF₃ O 3.197 H CMe═CFCF₃ Me CF₂H O 3.198 H CMe═CFCF₃ Me Me O 3.199 H CMe═CClCF₃ Me CF₃ O 3.200 H CMe═CClCF₃ Me CF₂H O 3.201 H CMe═CClCF₃ Me Me O 3.202 H CCF₃═CF₂ Me CF₃ O 3.203 H CCF₃═CF₂ Me CF₂H O 3.204 H CCF₃═CF₂ Me Me O 3.205 H CCF₃═CCl₂ Me CF₃ O 3.206 H CCF₃═CCl₂ Me CF₂H O 3.207 H CCF₃═CCl₂ Me Me O 3.208 H CCF₃═CBr₂ Me CF₃ O 3.209 H CCF₃═CBr₂ Me CF₂H O 3.210 H CCF₃═CBr₂ Me Me O 3.211 H CCF₃═CH₂ Me CF₃ O 3.212 H CCF₃═CH₂ Me CF₂H O 3.213 H CCF₃═CH₂ Me Me O 3.214 H CCF₃═CFBr Me CF₃ O 3.215 H CCF₃═CFBr Me CF₂H O 3.216 H CCF₃═CFBr Me Me O 3.217 H CCF₃═CHF Me CF₃ O 3.218 H CCF₃═CHF Me CF₂H O 3.219 H CCF₃═CHF Me Me O 3.220 H CCF₃═CFCl Me CF₃ O 3.221 H CCF₃═CFCl Me CF₂H O 3.222 H CCF₃═CFCl Me Me O 3.223 H CCF₃═CHCl Me CF₃ O 3.224 H CCF₃═CHCl Me CF₂H O 3.225 H CCF₃═CHCl Me Me O 3.226 H CH═CFCF₂Cl Me CF₃ O 3.227 H CH═CFCF₂Cl Me CF₂H O 3.228 H CH═CFCF₂Cl Me Me O 3.229 H CH═CClCF₂Cl Me CF₃ O 3.230 H CH═CClCF₂Cl Me CF₂H O 3.231 H CH═CClCF₂Cl Me Me O 3.232 H CH₂CF═CF₂ Me CF₃ O 3.233 H CH₂CF═CF₂ Me CF₂H O 3.234 H CH₂CF═CF₂ Me Me O 3.235 H CF═CFBr Me CF₃ O 3.236 H CF═CFBr Me CF₂H O 3.237 H CF═CFBr Me Me O 3.238 H CH₂CH═CF₂ Me CF₃ O 3.239 H CH₂CH═CF₂ Me CF₂H O 3.240 H CH₂CH═CF₂ Me Me O 3.241 H CH₂CH═CCl₂ Me CF₃ O 3.242 H CH₂CH═CCl₂ Me CF₂H O 3.243 H CH₂CH═CCl₂ Me Me O 3.244 H CH₂CH═CBr₂ Me CF₃ O 3.245 H CH₂CH═CBr₂ Me CF₂H O 3.246 H CH₂CH═CBr₂ Me Me O 3.247 H CCl═CF₂ Me CF₃ O 3.248 H CCl═CF₂ Me CF₂H O 3.249 H CCl═CF₂ Me Me O 3.250 H C≡CCMe₂OH Me CF₃ O 3.251 H C≡CCH₂CH₃ Me CF₂H O 3.252 H C≡CCH₂CH₃ Me Me O 3.253 H C≡CCH₂CH₃ Me CF₃ O 3.254 H C≡CCF═CF₂ Me CF₃ O 3.255 H C≡CCF═CF₂ Me CF₂H O 3.256 H C≡CCHFCl Me CF₃ O 3.257 H C≡CCHFCl Me CF₂H O 3.258 H C≡CCHFCl Me Me O 3.259 H CH═CFC₂F₅ Me CF₃ O 3.260 H CH═CFC₂F₅ Me CF₂H O 3.261 H CH═CFC₂F₅ Me Me O 3.262 H C≡CCF₂CH₂CH₃ Me CF₃ O 3.263 H C≡CCF₂CH₂CH₃ Me CF₂H O 3.264 H C≡CCF₂CH₂CH₃ Me Me O 3.265 H C≡CCHFCH₂CH₃ Me CF₃ O 3.266 H C≡CCHFCH₂CH₃ Me CF₂H O 3.267 H C≡CCHFCH₂CH₃ Me Me O 3.268 H C≡CCF(CF₃)₂ Me CF₃ O 3.269 H C≡CCF(CF₃)₂ Me CF₂H O 3.270 H C≡CCF(CF₃)₂ Me Me O 3.271 H CH═CClC₂F₅ Me CF₃ O 3.272 H CH═CClC₂F₅ Me CF₂H O 3.273 H CH═CClC₂F₅ Me Me O 3.274 H C≡CC₂F₅ Me CF₃ O 3.275 H C≡CC₂F₅ Me CF₂H O 3.276 H C≡CC₂F₅ Me Me O

Table 3 provides 276 compounds of fornula (Ic):

wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcA) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcB) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcC) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcD) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcE) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcF) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 3 provides 276 compounds of formula (IcG) wherein R¹, R⁷, R⁹, R¹⁰ and X are as defined in Table 3.

Table 4 provides 3 compounds of formula (Id):

wherein R¹, R⁷, R⁹ and R¹⁰ are as defined in Table 4. TABLE 4 Compound No. R¹ R⁷ R⁹ R¹⁰ 4.01 H C≡CH Me CF₃ 4.02 H C≡CSiMe₃ Me CF₃ 4.03 H CH═CH₂ Me CF₃

Table 5 provides 15 compounds of formula (Ie):

wherein R¹, R⁷, R⁸, R⁹ and R¹⁰ are as defined in Table 5. TABLE 5 Compound No. R¹ R⁷ R⁸ R⁹ R¹⁰ 5.01 H C≡CH H H CF₃ 5.02 H C≡CH Me Me Me 5.03 H C≡CH H Me CF₃ 5.04 H C≡CH Me Me H 5.05 COMe C≡CH Me Me H 5.06 COMe C≡CH Me Me Me 5.07 COEt C≡CH Me Me Me 5.08 H C≡CSiMe₃ H H CF₃ 5.09 H C≡CSiMe₃ Me Me Me 5.10 H C≡CSiMe₃ H Me CF₃ 5.11 H C≡CSiMe₃ Me Me H 5.12 H C≡CSiMe₃ H H CF₃ 5.13 H CH═CH₂ Me Me Me 5.14 H CH═CH₂ H Me CF₃ 5.15 H CH═CH₂ Me Me H

Table 6 provides 15 compounds of formula (If):

wherein R¹, R⁷, R⁸, R⁹ and R¹⁰ are as defined in Table 6. TABLE 6 Compound No. R¹ R⁷ R⁸ R⁹ R¹⁰ 6.01 H C≡CH H H CF₃ 6.02 H C≡CH Me Me Me 6.03 H C≡CH H Me CF₃ 6.04 H C≡CH Me Me H 6.05 COMe C≡CH Me Me H 6.06 COMe C≡CH Me Me Me 6.07 COEt C≡CH Me Me Me 6.08 H C≡CSiMe₃ H H CF₃ 6.09 H C≡CSiMe₃ Me Me Me 6.10 H C≡CSiMe₃ H Me CF₃ 6.11 H C≡CSiMe₃ Me Me H 6.12 H C≡CSiMe₃ H H CF₃ 6.13 H CH═CH₂ Me Me Me 6.14 H CH═CH₂ H Me CF₃ 6.15 H CH═CH₂ Me Me H

Table 7 provides 10 compounds of formula (Ig):

wherein R¹, R⁷, R⁸ and X are as defined in Table 7. TABLE 7 Compound No. R¹ R⁷ R⁸ X 7.01 H C≡CH CF₃ O 7.02 H C≡CH Me O 7.03 H C≡CH CF₃ S 7.04 COMe C≡CH Me O 7.05 H C≡CSiMe₃ CF₃ O 7.06 H C≡CSiMe₃ Me O 7.07 H CH═CH₂ CF₃ O 7.08 H CH═CH₂ CF₃ O 7.09 propargyl CH═CH₂ Me O 7.10 allenyl CH═CH₂ Me O

Table 8 provides 10 compounds of formulae (Ih):

wherein R¹, R⁷, R⁸ and X are as defined in Table 8. TABLE 8 Compound No. R¹ R⁷ R⁸ X 8.01 H C≡CH CF₃ O 8.02 H C≡CH Me O 8.03 H C≡CH CF₃ S 8.04 COMe C≡CH Me O 8.05 H C≡CSiMe₃ CF₃ O 8.06 H C≡CSiMe₃ Me O 8.07 H CH═CH₂ CF₃ O 8.08 H CH═CH₂ CF₃ O 8.09 propargyl CH═CH₂ Me O 8.10 allenyl CH═CH₂ Me O

TABLE 9 Compound No. R¹ R⁷ R⁸ 9.01 H C≡CH Cl 9.02 H C≡CH CF₃ 9.03 COMe C≡CH Cl 9.04 H C≡CH Br 9.05 COCH₂OMe C≡CH Cl 9.06 H C≡CSiMe₃ Cl 9.07 H C≡CSiMe₃ CF₃ 9.08 H C≡CSiMe₃ Br 9.09 H CH═CH₂ CF₃ 9.10 H CH═CH₂ Br 9.11 H CH═CH₂ Cl 9.12 H CH═CH₂ CH₃ 9.13 propargyl CH═CH₂ Cl 9.14 allenyl CH═CH₂ Cl 9.15 H C≡CCl Cl 9.16 H C≡CCl CF₃ 9.17 H C≡CCl Br 9.18 H C≡CBr Cl 9.19 H C≡CBr CF₃ 9.20 H C≡CBr Br 9.21 H C≡CCF₃ Cl 9.22 H C≡CCF₃ CF₃ 9.23 H C≡CCF₃ Br 9.24 H CH═CF₂ CF₃ 9.25 H CH═CF₂ Br 9.26 H CH═CF₂ Cl 9.27 H CCl═CH₂ CF₃ 9.28 H CCl═CH₂ Br 9.29 H CCl═CH₂ Cl 9.30 H CBr═CH₂ CF₃ 9.31 H CBr═CH₂ Br 9.32 H CBr═CH₂ Cl 9.33 H CF═CHF CF₃ 9.34 H CF═CHF Br 9.35 H CF═CHF Cl 9.36 H CH═CHCF₃ CF₃ 9.37 H CH═CHCF₃ Br 9.38 H CH═CHCF₃ Cl 9.39 H CH═CClCF₃ CF₃ 9.40 H CH═CClCF₃ Br 9.41 H CH═CClCF₃ Cl 9.42 H CH₂C≡CH CF₃ 9.43 H CH₂C≡CH Br 9.44 H CH₂C≡CH Cl 9.45 H CH₂C≡CSiMe₃ CF₃ 9.46 H CH₂C≡CSiMe₃ Br 9.47 H CH₂C≡CSiMe₃ Cl 9.48 H C≡CMe CF₃ 9.49 H C≡CMe Br 9.50 H C≡CMe Cl 9.51 H CH═CCl₂ CF₃ 9.52 H CH═CCl₂ Br 9.53 H CH═CCl₂ Cl 9.54 H CH═CHSiMe₃ CF₃ 9.55 H CH═CHSiMe₃ Br 9.56 H CH═CHSiMe₃ Cl 9.57 H C≡C(cyclopropyl) Cl 9.58 H SiMe₃ Cl 9.59 H C≡CCMe₃ Cl 9.60 H CH═CBr₂ CF₃ 9.61 H CH═CBr₂ Br 9.62 H CH═CBr₂ Cl 9.63 H CF═CF₂ CF₃ 9.64 H CF═CF₂ Br 9.65 H CF═CF₂ Cl 9.66 H C≡CCMe₃ CF₃ 9.67 H C≡CCMe₃ Br 9.68 allenyl C≡CCMe₃ Cl 9.69 H C≡C(cyclopropyl) CF₃ 9.70 H C≡C(cyclopropyl) Br 9.71 H C≡CF CF₃ 9.72 H C≡CF Br 9.73 H C≡CF Cl 9.74 H C≡CCF₂Cl Cl 9.75 H C≡CCF₂Cl CF₃ 9.76 H C≡CCF₂Cl Br 9.77 H C≡CCF₂H Cl 9.78 H C≡CCF₂H CF₃ 9.79 H C≡CCF₂H Br 9.80 H C≡CCF₂Br Cl 9.81 H C≡CCF₂Br CF₃ 9.82 H C≡CCF₂Br Br 9.83 H C≡CCH₂F Cl 9.84 H C≡CCH₂F CF₃ 9.85 H C≡CCH₂F Br 9.86 H C≡CCH(Me)F Cl 9.87 H C≡CCH(Me)F CF₃ 9.88 H C≡CCH(Me)F Br 9.89 H C≡CC(Me)₂F Cl 9.90 H C≡CC(Me)₂F CF₃ 9.91 H C≡CC(Me)₂F Br 9.92 H C≡CCH₂CMe₃ Cl 9.93 H C≡CCH₂CMe₃ Br 9.94 H C≡CCHMe₂ CF₃ 9.95 H C≡CCHMe₂ Br 9.96 H C≡CCHMe₂ Cl 9.97 H C≡CCH₂CHMe₂ CF₃ 9.98 H C≡CCH₂CHMe₂ Br 9.99 H C≡CCH₂CHMe₂ Cl 9.100 H CF₂C≡CMe CF₃ 9.101 H CF₂C≡CMe Br 9.102 H CF₂C≡CMe Cl 9.103 H CF₂C≡CH CF₃ 9.104 H CF₂C≡CH Br 9.105 H CF₂C≡CH Cl 9.106 H CHFC≡CH CF₃ 9.107 H CHFC≡CH Br 9.108 H CHFC≡CH Cl 9.109 H C≡C(1-F-cyclopentyl) CF₃ 9.110 H C≡C(1-F-cyclopentyl) Br 9.111 H C≡C(1-F-cyclopentyl) Cl 9.112 H C≡CCH₂OMe Cl 9.113 H C≡CCH₂OMe Br 9.114 H C≡CCH₂OMe CF₃ 9.115 H C≡CCMe₂OMe Cl 9.116 H C≡CCMe₂OMe Br 9.117 H C≡CCMe₂OMe CF₃ 9.118 H C≡CCMe₂OCOMe Cl 9.119 H C≡CCMe₂OCOMe Br 9.120 H C≡CCMe₂OCOMe CF₃ 9.121 H C≡CCF₂Me Cl 9.122 H C≡CCF₂Me Br 9.123 H C≡CCF₂Me CF₃ 9.124 H CH═CFCl CF₃ 9.125 H CH═CFCl Br 9.126 H CH═CFCl Cl 9.127 H CH═CFBr CF₃ 9.128 H CH═CFBr Br 9.129 H CH═CFBr Cl 9.130 H CH═CHBr CF₃ 9.131 H CH═CHBr Br 9.132 H CH═CHBr Cl 9.133 H CMe═CHCF₃ CF₃ 9.134 H CMe═CHCF₃ Br 9.135 H CMe═CHCF₃ Cl 9.136 H CH═CFCF₃ CF₃ 9.137 H CH═CFCF₃ Br 9.138 H CH═CFCF₃ Cl 9.139 H CH═CBrCF₃ CF₃ 9.140 H CH═CBrCF₃ Br 9.141 H CH═CBrCF₃ Cl 9.142 H CH═CHC₂F₅ CF₃ 9.143 H CH═CHC₂F₅ Br 9.144 H CH═CHC₂F₅ Cl 9.145 H CH═CHCl CF₃ 9.146 H CH═CHCl Br 9.147 H CH═CHCl Cl 9.148 H CH═C(CF₃)₂ Cl 9.149 H CMe═CFCl CF₃ 9.150 H CMe═CFCl Br 9.151 H CMe═CFCl Cl 9.152 H CMe═CFBr CF₃ 9.153 H CMe═CFBr Br 9.154 H CMe═CFBr Cl 9.155 H CMe═CF₂ CF₃ 9.156 H CMe═CF₂ Br 9.157 H CMe═CF₂ Cl 9.158 H CMe═CCl₂ CF₃ 9.159 H CMe═CCl₂ Br 9.160 H CMe═CCl₂ Cl 9.161 H CMe═CBr₂ CF₃ 9.162 H CMe═CBr₂ Br 9.163 H CMe═CBr₂ Cl 9.164 H CCF₃═CF₂ CF₃ 9.165 H CCF₃═CF₂ Br 9.166 H CCF₃═CF₂ Cl 9.167 H CCF₃═CCl₂ CF₃ 9.168 H CCF₃═CCl₂ Br 9.169 H CCF₃═CCl₂ Cl 9.170 H CCF₃═CBr₂ CF₃ 9.171 H CCF₃═CBr₂ Br 9.172 H CCF₃═CBr₂ Cl 9.173 H CCF₃═CH₂ CF₃ 9.174 H CCF₃═CH₂ Br 9.175 H CCF₃═CH₂ Cl 9.176 H CCF₃═CFBr CF₃ 9.177 H CCF₃═CFBr Br 9.178 H CCF₃═CFBr Cl 9.179 H CCF₃═CFCl CF₃ 9.180 H CCF₃═CFCl Br 9.181 H CCF₃═CFCl Cl 9.182 H CH═CFCF₂Cl CF₃ 9.183 H CH═CFCF₂Cl Br 9.184 H CH═CFCF₂Cl Cl 9.185 H CH═CClCF₂Cl Cl 9.186 H CH₂CF═CF₂ CF₃ 9.187 H CH₂CF═CF₂ Br 9.188 H CH₂CF═CF₂ Cl 9.189 H CF═CFBr Cl 9.190 H CH₂CH═CF₂ Cl 9.191 H CH₂CH═CCl₂ Cl 9.192 H CH₂CH═CBr₂ Cl 9.193 H CH₂CH═CBr₂ CF₃ 9.194 H CH₂CH═CBr₂ Br 9.195 H CCl═CF₂ Cl 9.196 H C≡CMe CHF₂ 9.197 H C≡CCHMe₂ CHF₂ 9.198 H C≡CCH₂CHMe₂ CHF₂ 9.199 H C≡CCF₃ CHF₂ 9.200 H C≡CH CHF₂ 9.201 H C≡CCH₂SiMe₃ Cl 9.202 H C≡CCH₂CF₃ Cl 9.203 H C≡CSi(Me)₂CMe₃ Cl 9.204 H C≡CCH₂CH₃ Cl 9.205 H C≡CCF═CF₂ Cl 9.206 H C≡CCHFCl Cl 9.207 H CH═CFC₂F₅ Cl 9.208 H C≡CCF₂CH₂CH₃ Cl 9.209 H C≡CCHFCH₂CH₃ Cl 9.210 H C≡CCF(CF₃)₂ Cl 9.211 H CH═CClC₂F₅ Cl 9.212 H C≡CC₂F₅ Cl

Table 9 provides 212 compounds of formula (Ii):

wherein R¹, R⁷ and R⁸ are as defined in Table 9.

Table 9 provides 212 compounds of formula (IiA) wherein R¹, R⁷ and R⁸ are as defined in Table 9.

Table 9 provides 212 compounds of formula (IiB) wherein R¹, R⁷ and R⁸ are as defined in Table 9.

Table 9 provides 212 compounds of formula (IiC) wherein R¹, R⁷ and R⁸ are as defined in Table 9.

Table 9 provides also 212 compounds of formula (IiD) wherein R¹, R⁷ and R⁸ are as defined in Table 9.

Table 10 provides 14 compounds of formula (Ij):

wherein R¹, R⁷ and R⁸ are as defined in Table 10. TABLE 10 Compound No. R¹ R⁷ R⁸ 10.01 H C≡CH Cl 10.02 H C≡CH CF₃ 10.03 COMe C≡CH Cl 10.04 H C≡CH Br 10.05 COCH₂OMe C≡CH Cl 10.06 H C≡CSiMe₃ Cl 10.07 H C≡CSiMe₃ CF₃ 10.08 H C≡CSiMe₃ Br 10.09 H CH═CH₂ CF₃ 10.10 H CH═CH₂ Br 10.11 H CH═CH₂ Cl 10.12 H CH═CH₂ CH₃ 10.13 propargyl CH═CH₂ Cl 10.14 allenyl CH═CH₂ Cl

Table 11 provides 14 compounds of formula (Ik):

wherein R¹, R⁷ and R⁸ are as defined in Table 11. TABLE 11 Compound No. R¹ R⁷ R⁸ 11.01 H C≡CH Cl 11.02 H C≡CH CF₃ 11.03 COMe C≡CH Cl 11.04 H C≡CH Br 11.05 COCH₂OMe C≡CH Cl 11.06 H C≡CSiMe₃ Cl 11.07 H C≡CSiMe₃ CF₃ 11.08 H C≡CSiMe₃ Br 11.09 H CH═CH₂ CF₃ 11.10 H CH═CH₂ Br 11.11 H CH═CH₂ Cl 11.12 H CH═CH₂ CH₃ 11.13 propargyl CH═CH₂ Cl 11.14 allenyl CH═CH₂ Cl

Table 12 provides 94 compounds of formula (II) where R², R³, R⁴ and R⁵ are each hydrogen; n is 0; and R¹ and R⁷ are as defined in Table 12. TABLE 12 Compound No. R¹ R⁷ 12.01 H C≡CH 12.02 H C≡CSiMe₃ 12.03 H C≡CCF₃ 12.04 H C≡CCl 12.05 H CH═CH₂ 12.06 H CH═CF₂ 12.07 H CH═CCl₂ 12.08 H CH═CBr₂ 12.09 H CF═CF₂ 12.10 H CCl═CH₂ 12.11 H CF═CHF 12.12 H CH═CHCF₃ 12.13 H CH═CClCF₃ 12.14 H CH₂C≡CH 12.15 H C≡CCMe₃ 12.16 CHO C≡CMe 12.17 H C≡C(cyclopropyl) 12.18 H SiMe₃ 12.19 H C≡CBr 12.20 H CBr═CH₂ 12.21 H CH═CHSiMe₃ 12.22 H CH₂C≡CSiMe₃ 12.23 H C≡CMe 12.24 H C≡CF 12.25 H C≡CCF₂Cl 12.26 H C≡CCF₂H 12.27 H C≡CCF₂Br 12.28 H C≡CCH₂F 12.29 H C≡CCH(Me)F 12.30 H C≡CC(Me)₂F 12.31 H C≡CCH₂C(Me)₃ 12.32 H C≡CCH(Me)₂ 12.33 H C≡CCH₂CH(Me)₂ 12.34 H CH₂C≡CCMe₃ 12.35 H CF₂C≡CCMe₃ 12.36 H CF₂C≡CMe 12.37 H CF₂C≡CH 12.38 H CMe₂C≡CH 12.39 H CHFC≡CH 12.40 H CHMeC≡CH 12.41 H CH(CF₃)C≡CH 12.42 H C≡C(1-F-cyclopentyl) 12.43 H C≡CCH₂OMe 12.44 H C≡CCMe₂OMe 12.45 H C≡CCMe₂OCOMe 12.46 H C≡CCF₂Me 12.47 H C≡CC(Me)═CH₂ 12.48 H CH═CFCl 12.49 H CH═CFBr 12.50 H CH═CHBr 12.51 H CH═CHF 12.52 H CMe═CHCF₃ 12.53 H CH═CFCF₃ 12.54 H CH═CBrCF₃ 12.55 H CH═CHC₂F₅ 12.56 H CH═CHCl 12.57 H CH═C(CF₃)₂ 12.58 H CMe═CFCl 12.59 H CMe═CFBr 12.60 H CMe═CF₂ 12.61 H CMe═CCl₂ 12.62 H CMe═CBr₂ 12.63 H CMe═CFCF₃ 12.64 H CMe═CClCF₃ 12.65 H CCF₃═CF₂ 12.66 H CCF₃═CCl₂ 12.67 H CCF₃═CCl₂ 12.68 H CCF₃═CCl₂ 12.69 H CCF₃═CBr₂ 12.70 H CCF₃═CH₂ 12.71 H CCF₃═CFBr 12.72 H CCF₃═CHF 12.73 H CCF₃═CFCl 12.74 H CCF₃═CHCl 12.75 H CH═CFCF₂Cl 12.76 H CH═CClCF₂Cl 12.77 H CH₂CF═CF₂ 12.78 H CF═CFBr 12.79 H CH₂CH═CF₂ 12.80 H CH₂CH═CCl₂ 12.81 H CH₂CH═CBr₂ 12.82 H CCl═CF₂ 12.83 H C≡CCH₂SiMe₃ 12.84 H C≡CSiMe₂CMe₃ 12.85 H C≡CCMe₂OH 12.86 H C≡CCH₂CH₃ 12.87 H C≡CCF═CF₂ 12.88 H C≡CCHFCl 12.89 H CH═CFC₂F₅ 12.90 H C≡CCF₂CH₂CH₃ 12.91 H C≡CCHFCH₂CH₃ 12.92 H C≡CCF(CF₃)₂ 12.93 H CH═CClC₂F₅ 12.94 H C≡CC₂F₅

Table 13 provides 1 compound of formula (m) where R², R³, R⁴ and R⁵ are each hydrogen; n is 0; and Hal and R⁷ are as defined in Table 13. TABLE 13 Compound Number R⁷ Hal 13.01 C≡CH Br

Throughout this description, temperatures are given in degrees Celsius; “NMR” means nuclear magnetic resonance spectrum; MS stands for mass spectrum; M⁺−1 or M⁺1 are signals in the mass spectrum respectively corresponding to the molecular weight minus 1 or the molecular weight plus 1; and “%” is percent by weight, unless corresponding concentrations are indicated in other units.

The following abbreviations are used throughout this description: m.p. = melting point b.p. = boiling point. s = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet ppm = parts per million

Table 14 shows selected melting point, selected molecular ion and selected NMR data, all with CDCl₃ as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDCl₃/d₆-DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 13. Unless otherwise stated, the data relate to a cis/trans mixture of each compound. TABLE 14 Compound ¹H-NMR data: (ppm/multiplicity/number of Hs) Number or MS-data m.p./(° C.) 1.01 169-170 1.03 132-135 1.08 147-150 1.10 >200 1.12 195-197 1.13 139-144 1.15 193-194 1.16 120-125 1.18 207-209 1.19 210-212 1.22 184-187 1.24 137-141 1.29 197-198 1.30 181-182 1.32 173-176 1.33 147-150 1.35 167-169 1.36 148-150 1.38 156-157 1.39 168-170 1.41 212-213 1.42 174-176 1.50 117-124 1.53 205-206 1.54 194-195 1.56 143-145 1.57 118-121 1.59 186-190 1.60 137-139 1.66 139-143 1.67 406(M⁺−1) 193-196 1.69 382(M⁺−1) 221-223 1.70 364(M⁺−1) 205-208 1.77 208-210 1.78 202-205 1.80 165-166 1.81 165-169 1.85   198-198.5 1.86   184-184.5 1.88 206-207 1.89 200-201 1.193 160-162 1.94 205-206 1.95 198-199 1.97 197-198 (decomposition) 1.98 176-177 1.100 120-121 1.101 128-129 1.106 155-158 1.107 142-143 1.109 150-153 1.110 132-140 1.137 132-133 1.138 167-169 1.139 163-165 1.141   141-142.5 1.142 155-156 1.144 1.8(s, 6); 2.1(s, 3); 3.95(s, 3) 7.2-7.6(m, 7); 7.75(br.s, 1); 8.25(d, 1) 1.145 132-141 1.147 149-150 1.150 143-145 1.151 189-194 1.152 168-170 1.154 197-200 1.155 174-178 1.158   195 1.166 172-155 1.167 145-150 1.182 127-129 1.185 111-114 1.194 2.25(s, 3); 3.9(s, 3); 6.7(t, 1); 7.2-7.5(m, 6); 7.7(s, 1); 7.72(br, 1); 8.3(d, 1) 1.212 176-179 1.226 152.5-153   1.227 146-147 1.250 159-162 1.251 156-161 1.252 163-165 1.254 139-140 1.255   187-187.5 1.257 177-178 2.01 145-148 2.08 148-154 2.66 160-165 3.01 145-147 3.08 103-105 3.12 122-126 3.18 160-165 3.29 146-147 3.32 125-130 3.35 120-126 3.38 122-127 3.41 169-170 3.56 132-137 3.66 129-133 3.69 159-163 3.97 133-134 3.100 127.7-129   3.109 117-119 3.136 140-142 3.141 1.55(s, 6); 2.7(s, 3); 3.4(s, 3); 7.2-7.3(m, 4); 7.4(m, 1); 7.5(d, 2); 7.55(br, 1); 8.3(d, 1) 3.146 141-142 3.157 145-157 3.166 148-150 3.193 128-132 3.211 183-184 3.250 140-143 9.01 150-152 9.06 84-86 9.15 154-157 9.21 185-189 9.38 141-142 9.41 143-145 9.50 157-159 9.53 133-138 9.58 130-132 9.59 123-125 9.62 138-139 9.65 164-167 9.68 1.8(s, 9); 4.9+5.25(m, 1); 6.15-8.5(m, 12) 9.83 143-145 9.86 169-170 9.89   167-167.5 9.99 109-111 9.118 1.8(s, 6); 2.1(s, 3); 7.2-7.6(m, 9), 8.1(m, 1); 8.45(m, 1) 9.132 162-165 9.138 172-175 9.163 167-171 9.185   119-120.5 9.201 0.0(s, 9); 1.55(s, 2); 7.0-7.3(m, 8); 79-8.0(m, 2); 8.3(m, 2) 9.203 105-107 12.01 111-115 12.02 0.05(s, 9); 6.5-6.7(d+t, 2); 6.8-7.1(t+t, 2); 7.2-7.5(m, 4) 12.03 262(M+H⁺); 303(M+MeCN+H⁺); 12.04 92-98 12.06 3.75(br, 2); 5.35(dd, 1); 6.75-6.9(m, 2); 7.1-7.2(m, 2); 7.35-7.5(m, 4) 12.07 3.8(br, 2); 6.8(d, 1); 6.85(t, 1); 6.9(s, 1); 7.1-7.2(d+t, 2); 7.45-7.65(m, 4) 12.08 3.8(br, 2); 6.75-6.9(m, 2); 7.1-7.2(m, 2); 7.5-7.7(m, 5) 12.09 3.8(br, 2); 6.7-6.9(m, 2); 7.1-7.2(m, 2); 7.6(very narrow m, 4) ¹⁹F: −99.7; −114.6; −177.3 12.10 230(M+H⁺); 371(M+MeCN+H⁺) 12.12 84-86 12.13 298(M+H⁺); 339(M+MeCN+H⁺); 12.14 208(M+H⁺); 249(M+MeCN+H⁺); 12.15 66-69 12.16 91-96 12.17 0.8-0.9(m, 4); 1.4-1.5(m, 2); 3.7(br, 2); 6.7-6.8(m, 2); 7.1-7.2(m, 2); 7.3-7.5(m, 4) 12.18 0.15(s, 9); 2.0-2.6(very broad, 2); 6.6-6.7(m, 2); 7.0-7.1(m, 2); 7.3-7.5(m, 4) 12.19 3.8(br, 2); 6.75-6.9(m, 2); 7.1-7.2(m, 2); 7.35-7.55(m, 4) 12.23 108-112 12.25 3.75(br, 2); 6.8(m, 2); 7.1-7.25(m, 2); 7.5-7.7(m, 4) ¹⁹F: −35.9 12.26 3.8(br, 2); 6.4(t, 1); 6.75-6.9(m, 2); 7.1-7.25(m, 2); 7.4-7.56(m, 4); ¹⁹F: −105.7 12.28 69-71 12.29 1.7(d of d, 3); 3.8(br, 2); 5.5(d of quartetts, 1); 6.75-6.9(m, 2); 7.05-7.2(m, 2); 7.4-7.6(m, 4) ¹⁹F: −165.6 12.30 1.75(d, 6); 3.8(br, 2); 6.8(m, 2); 7.15(m, 2); 7.4-7.6(m, 4) ¹⁹F: −126.0 12.32 1.3(d, 6); 3.7(br, 2); 6.7-6.8(d+t, 2); 7.15(m, 2); 7.3-7.5(m, 4) 12.33 1.05(d, 6); 1.9(m, 1); 2.35(d, 2); 3.75(br, 2); 6.75-6.9(m, 2); 7.1-7.2(m, 2); 7.35-7.5(m, 4) 12.42 1.7-2.5(m, 8); 3.7(br, 2); 6.7-6.8(m, 2); 7.05-7.15(m, 2); 7.35.7.5(m, 4); 7.1-7.2(m, 2); 7.4-7.6(m, 4) 12.43 3.45(s, 3); 3.8(br, 2); 4.35(s, 2); 6.7-6.8(d+t, 2); 7.1-7.25(m, 2); 7.4-7.6(m, 4) 12.45 1.75(s, 6); 2.1(s, 3); 3.75(br, 2); 6.75-6.85(m, 2); 7.1-7.2(m, 2); 7.4-7.6(m, 4) 12.46 2.0(t, 3); 3.75(br, 2); 6.75-6.85(m, 2); 7.1-7.2(m, 2); 7.4-7.6(m, 4) 12.47 2.0(s, 3); 3.75(br, 2); 5.3(narrow m, 1); 5.4(s, 1); 6.75-6.85(m, 2); 7.1-7.2(m, 2); 7.4-7.55(m, 4) 12.48 3.8(br, 2); 5.85+6.45(2ds, 1); 6.7-6.9(m, 2); 7.1-7.2(m, 2); 7.4-7.65(m, 4); ¹⁹F: −71.2; −73.9 12.49 4.0-4.6(br, 2); 6.0+6.7(2ds, 1); 6.75-6.9(m, 2); 7.1-7.2(m, 2); 7.4-7.65(m, 4); 12.50 86-92 12.53 12.58 2.1(2s, 3); 3.8(br, 2); 6.7-6.9(m, 2); 7.1-7.2(m, 2); 7.35-7.5(m, 2); ¹⁹F: −80.1; −81.3 12.59 2.1(2s, 3); 3.8(br, 2); 6.7-6.9(m, 2); 7.1-7.2(m, 2); 7.35-7.5(m, 2); ¹⁹F: −74.2; −74.6 12.62 120-129 12.70 3.75(br, 2); 5.8(narrow m, 1); 5.95(narrow m, 1); 6.75-6.9(m, 2); 7.1-7.2(m, 2); 7.4-7.55(m, 4) 12.75   67-68.5 12.83 0.0(s, 9); 1.6(s, 2); 6.6(d, 1); 6.65(t, 1); 7.0(m, 2); 7.2-7.4(m, 4) 12.84 0.0(s, 6); 0.8(s, 9); 4.25(very broad, 2); 6.65-6.75(m, 2); 6.9-7.05(m, 2); 7.2-7.4(m, 4) 12.85 252(M+H⁺) 15.25 131-134 15.26 Amorphous 15.28 1.3(s, 9); 7.2-7.5(m, 10); 8.1(m, 2); 8.45(m, 2) 16.7 63-64

Table 15 provides 48 compounds of formulas 1(m) where R, X and Het are as defined in Table 15.

TABLE 15 Compound No. X R Het 15.1 H C≡CH Het(1) 15.2 H C≡CH Het(2) 15.3 H C≡CH Het(3) 15.4 H C≡CH Het(4) 15.5 Cl C≡CH Het(1) 15.6 Cl C≡CH Het(2) 15.7 Cl C≡CH Het(3) 15.8 Cl C≡CH Het(4) 15.9 F C≡CH Het(1) 15.10 F C≡CH Het(2) 15.11 F C≡CH Het(3) 15.12 F C≡CH Het(4) 15.13 H C≡CMe Het(1) 15.14 H C≡CMe Het(2) 15.15 H C≡CMe Het(3) 15.16 H C≡CMe Het(4) 15.17 F C≡CMe Het(1) 15.18 F C≡CMe Het(2) 15.19 F C≡CMe Het(3) 15.20 F C≡CMe Het(4) 15.21 Cl C≡CMe Het(1) 15.22 Cl C≡CMe Het(2) 15.23 Cl C≡CMe Het(3) 15.24 Cl C≡CMe Het(4) 15.25 H C≡CCMe₃ Het(1) 15.26 H C≡CCMe₃ Het(2) 15.27 H C≡CCMe₃ Het(3) 15.28 H C≡CCMe₃ Het(4) 15.29 Cl C≡CCMe₃ Het(1) 15.30 Cl C≡CCMe₃ Het(2) 15.31 Cl C≡CCMe₃ Het(3) 15.32 Cl C≡CCMe₃ Het(4) 15.33 F C≡CCMe₃ Het(1) 15.34 F C≡CCMe₃ Het(2) 15.35 F C≡CCMe₃ Het(3) 15.36 F C≡CCMe₃ Het(4) 15.37 H CH═CClCF₃ Het(1) 15.38 H CH═CClCF₃ Het(2) 15.39 H CH═CClCF₃ Het(3) 15.40 H CH═CClCF₃ Het(4) 15.41 Cl CH═CClCF₃ Het(1) 15.42 Cl CH═CClCF₃ Het(2) 15.43 Cl CH═CClCF₃ Het(3) 15.44 Cl CH═CClCF₃ Het(4) 15.45 F CH═CClCF₃ Het(1) 15.46 F CH═CClCF₃ Het(2) 15.47 F CH═CClCF₃ Het(3) 15.48 F CH═CClCF₃ Het(4)

Table 16 provides 12 compounds of formulas II(m) where R and X are as defined in Table 16:

TABLE 16 Compound No. X R 16.1 H C≡CH 16.2 Cl C≡CH 16.3 F C≡CH 16.4 H C≡CMe 16.5 F C≡CMe 16.6 Cl C≡CMe 16.7 H C≡CCMe₃ 16.8 Cl C≡CCMe₃ 16.9 F C≡CCMe₃ 16.10 H CH═CClCF₃ 16.11 Cl CH═CClCF₃ 16.12 F CH═CClCF₃

The compounds according to the present invention may be prepared according to the following reaction schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).

There are a number of alternative methods for preparing a compound of formula (I).

Method A

A compound of formula (I) may be prepared by reacting a compound of formula (II) with a compound of formula Het—C(═O)OR′ (where R′ is C₁₋₅ alkyl) in the presence of strong base [for example NaH or sodium hexamethyldisilazane], in a dry polar solvent [preferably THF] and at a temperature between −10° C. and the boiling point of the solvent [preferably at ambient temperature]. The article by J. Wang et al, Synlett 2001, 1485 provides details of analogous preparations.

Method B

A compound of formula (I) may be prepared by reacting a compound of formula (II) with a compound of formula Het-C(═O)R″ [where R″ is OH or a leaving group, such as Cl, Br, F or OC(═O)C₁₋₄ alkyl] in an inert organic solvent [such as ethylacetate, dichloromethane, dioxane or DMF] and at a temperature between −10° C. and the boiling point of the solvent [preferably at ambient temperature]. If R″ is OH, the reaction is carried out in the presence of an activating agent [for example BOP-Cl] and two equivalents of a base [such as a tertiary amine, an inorganic carbonate or a hydrogen carbonate]. Alternatively, if R″ is a leaving group, the reaction is carried out in the presence of at least one equivalent of base [such as pyridine, a tertiary amine, an inorganic carbonate or a hydrogen carbonate].

Method C

A compound of formula (I) [where R¹ is as defined above but is not hydrogen] may be prepared by reacting a compound of formula (I) [where R¹ is hydrogen] with a compound of formula R¹-L¹ [where R¹ is as defined above but is not hydrogen; and L¹ is a leaving group such as Cl, Br, I, a sulfonate (for example a mesylate or a tosylate) or OC(O)C₁₋₄alkyl] in a solvent [such as a halogenated solvent (for example dichloromethane), an ether, ethylacetate, DMF or even water (as a biphasic rnixture, optionally in the presence of a phase transfer catalyst such as tetrabutylammonium hydrogensulfate)] and in the presence of a base [such as a tertiary amine, an alkali carbonate, an alkali bicarbonate, an alkali hydroxide or NaH; though if L¹ is O(CO) C₁₋₄ alkyl then simply heating without base is possible].

Method D

A compound of formula (I) may be prepared by reacting a compound of formula (Im) [where Hal is preferably bromo or iodo] with a compound of formula Het-C(═O)NH₂ in the presence of a Cu(I) compound and an aprotic solvent [such as a cyclic ether, for example dioxane] at an elevated temperature and preferably at reflux. The preferred conditions are CuI used at 2% to 100% mole/mole, relative to the compound of formula (III), in the presence of a 1,2-diamine as a ligand-forming substance (such as 1,2-diamino cyclohexane or ethylene diamnine) and at least 1 equivalent of a base (such as an alkali carbonate or an alkali phosphate. The article by A. Klapars et al. J. Am. Chem. Soc. 123, 7727 (2001) provides details of analogous preparations.

Method E

A compound of formula (I) may be prepared by conversion of a compound of formula (IV)

[where FG is a finctional group which is convertible to R⁷ in one or more synthetic steps]. Functional group interconversions are standard procedures for a person skilled in the art. There are many methods described in the literature, which can be used as such or with modifications according to the finctionalities present; Table A gives literature references (some of which also cite further appropriate references) which are specifically relevant to the preparation of a compound of formula (D) by the interconversion of FG to R⁷. It is apparent to the person skilled in the art that the literature examples given in Table A are not necessarily limited to the preparation of the specifically mentioned R⁷ but can be also applied by analogy to the preparation of other structurally related R⁷ TABLE A Reference FG R⁷ Synthesis 2001, 2081 CHO CH═CBr₂ Tetrahedron 58, 1491 (2002) CH═CHBr C≡CBr Russ. Chem. Bull. 50(6), CHO CH═CCl₂ 1047 (2001) Tetrahedron 57, 7519 (2001) CHO CH═CClCF₃ CH═CFCF₂Cl Bull. Chem. Soc. Jpn. 73, CHO CF═CBrF 1691 (2000) Bull. Chem. Soc. Jpn. 71, 2903 (1998-) J. Chem. Soc. Perkin 1 2002, 883 COCH₃ C(CH₃)═CHBr C(CH₃)═CCl₂ J. Fluorine Chem. 1, 381 (1972) COCH₃ C(CH₃)═CBr₂ J. Fluorine Chem. 23, 339 (1983) COCF₃ C(CH₃)═CFBr C(CH₃)═CFCl C(CF₃)═CFBr C(CF₃)═CFCl C(CF₃)═CF₂ Tetrahedron Letters 41, Hal CF═CHF 8045 (2000) J. Org. Chem. 62, 9217 (1997) Tetrahedron Letters 37, Hal CH═CF₂ 8799 (1996) JP 09278688 Hal CF═CF₂ J. Fluorine Chem. 31, 115 (1986) Zh. Org. Khim. 25, 1451 (1989) Hal CF═CFCl J. Org. Chem. 53, 2714 (1988) Hal CF═CFCF₃ J. Org. Chem. 56, 7336 (1991) Hal C(CF₃)═CH₂ Tetrahedron Letters 42, 4083 (2001) Ukr. Khim. Zh. 32, 996 (1966) CHBrCH₂CF₃ CH═CHCF₃ Bull. Chem. Soc. Jap. 62, 1352 CH═CClCF₃ C≡CCF₃ CH═CFCF₂Cl C≡CCF₂Cl J. Org. Chem. 54, 5856 (1989) Hal or triflate C≡CH J. Am. Chem. Soc. 109, C≡CSiMe₃ 2138 (1987) Tetrahedron 45, 6511 (1989) C≡CCH₃ J. Orgmet. Chem. 549, 127 (1997) C≡CCMe₃ Tetrahedron 56, 10075 (2000) C≡CCH₂OH Tetrahedron Asymmetry 6, C≡CCHMeOH 245 (1995) C≡CCMe₂OH C≡CCHO C≡CC(O)Me J. Org. Chem. 32, 1674 (1967) C≡CCH₃ CH₂C≡CH Synth. Comm. 1989, 561 CHO C≡CH CH₂CHO CH₂C≡CH WO 01 092563 CHO CH═CH₂ J. Am. Chem. Soc. 123, Hal or triflate CH═CH₂ 4155 (2001) Org. Lett. 2, 3703 (2000) J. Org. Chem. 57, 3558 (1992) Synthesis 2001, 893 GB 2 183 639 C≡CH CH═CH₂ Synthesis 1996, 1494 CHO C≡CCl J. Org. Chem. 49, 294 (1984) C≡CH C≡CBr US 6 159956 CH₂Br CH₂CF═CF₂ Liebigs Ann. Chem. 1995, 2027 CH₂Br CH═C(CF₃)₂ J. Am. Chem. Soc. 123, CH₂Br CH₂C≡CSiMe₃ 4155 (2001) Inorg. Chim. Acta 296, 37 (1999) Hal CH₂C≡CMe₃ J. Fluorine Chem. 111, 185 (2001) CH═CHBr CH═CHCF₃ J. Chem. Soc. Perkin I 1988, 921 CH═CFBr CH═CFCF₃ CH═CBr₂ CH═C(CF₃)₂ DE 4417441 C≡CCH₂OH C≡CCH₂F U.S. Pat. No. 3976691 C≡CCHMeOH C≡CCHMeF J. Org. Chem. 64, 7048 (1999) C≡CCMe₂OH C≡CCMe₂F C≡CCHO C≡CCHF₂ C≡CC(O)Me C≡CCF₂Me J. Chem. Soc. Perkin I 1994, 725 C≡CCH₂OH C≡CCH₂CF₃ Synthesis 1997, 1489 C≡CH C≡CCF₂CF₃ Angew. Chem. Int. Ed. 39, CH═CHCF₂CF₃ 2481 (2000) J. Org. Chem. 47, 2255 (1982) J. Fluorine. Chem. 113, 55 (2002) J. Fluorine. Chem. 64, 61(1993) C≡CH C≡CCHFCl J. Am. Chem. Soc. 109, C≡CCF₂Br 3492 (1987) J. Am. Chem. Soc. 107, CH═CHBr CH═CHCF₂CF₃ 5186 (1985)

There are a number of alternative methods for preparing a compound of formula (II), (III) or (IV).

A compound of formula (II), (III) or (VI) may be prepared, by functional group interconversion, from a compound of formula (V) [where FG is as defined above for a compound of formula (IV) and T is either halogen, amino, NHR¹, a protected amino group T′ (for example a carbamate, an amide, a cyclic imide, an N-alkyl-, N-alkenyl-, N-benzyl-, N-diphenylmethyl- or N-trityl-derivative, an imine derivative or an N-silyl- or N-disilyl-derivative) or a group T″ (that is, a group which may be converted to NH₂ or NHR¹ by applying synthetic methodology described in the literature; T″ being preferably azido, nitro, halogen, triflate, CONH₂, COOH, COCl or NCO)]. Starting from a compound of formula (V) the functional group FG may be converted to R⁷ by applying a method analogous to method E above. This conversion leads directly to a compound of formula (III) [when T is NHR₁], to a compound of formula (III) [when T is halogen (preferably chloro, bromo or iodo)] or to a compound of formula (VI) [when T is T′ or T″].

In a second step a compound of formula (VI) or (II) [when R¹ is other than H] can be converted to a compound of formula (II) [where R¹ is H] by either applying the methods [that is, deprotection or conversion of T″ to NH₂] as generically described above.

Examples of versatile values for T′ plus methods for deprotection are given in T. W. Green and P. Wuts, Protective Groups in Organic Synthesis, 3^(rd) edition (John Wiley & Sons 1999), Chapter 7.

Compilations of useful values for T″ plus literature to convert T″ into NH₂, T′ or NHR¹ can be found in M. B. Smith, Compendium of Organic Synthetic Methods, Vols. 1-10, Chapter 7 (Wiley, Vol. 10: 2002).

A compound of formula (II), (III) or (VI) may be prepared by a coupling reaction between a compound of formula (VII) and a compound of formula (VIII) [where Ra and Ra′ are each, independently, halogen (preferably Cl, Br or I), triflate or a metal-containing functionality containing, for example, B, Sn, Mg, Zn or Cu as the metal; examples are B(OH)₂, esters of boronic acid (preferably esters derived from 1,2- or 1,3-diols), trialkyltin (preferably Sn(CH₃)₃ or Sn(nBu)₃), a halogen salt of Mg, a halogen salt of Zn or Cu. If either Ra or Ra′ is a metal containing functionality, the other substituent must be halogen or triflate.

Such coupling reactions are widely known in the literature. Especially suitable are the Pd(0), Ni(0), or copper catalysed couplings which are well known to the person skilled in the art as Stille coupling, Suzuki coupling, Negishi coupling or Ullmann reaction. A comprehensive review. of these reactions can be found in Metal-Catalysed Cross-Coupling Reactions; F. Diederich and P. Stang (eds.); Wiley-VCH; Weinheim 1998.

In a second step a compound of formula (VI) or (II) [when R¹ is other than H] can be converted to a compound of formula (II) [where R¹ is H] by either applying the methods [that is, deprotection or conversion of T″ to NH₂] as generically described above.

Surprisingly, it has now been found that the novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.

The compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

Furthermore the compounds according to present invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management, etc.

The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Altemaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.) and rust (Puccinia spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).

Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.

The compounds of formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).

A preferred method of applying a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation [that is, a composition containing the compound of formula (I)] and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.

Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seed drenching agent, convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The following non-limiting Examples illustrate the above-described invention in more detail.

EXAMPLE 1

This Example illustrates the preparation of Compound No. 1.01.

2-Amino-4′-ethinyl-biphenyl (0.30 g) and 1-methyl-3-trifluoromethyl-4-chlorocarbonyl-pyrazol (0.33 g) were combined in THF under cooling with ice and then pyridine (0.12 ml) was added. After warming to ambient temperature the suspension was stirred for 3.5 hours, poured into water and extracted twice with ethylacetate. Separation of the organic phase, drying with sodium sulfate and evaporation of the solvent and chromatographic purification on silica gel (solvent: hexane:ethylacetate 2:1) yielded 0.4 g (70.2%) of Compound No. 1.01.

EXAMPLE 2

This Example illustrates the preparation of Compound No. 2.01.

To 1-methyl-3-trifluoromethyl-4-pyrrol carboxylic acid (0.22 g) dissolved in 10 ml dichloromethane were added triethylamine (0.32 ml) and 2-amino-4′-trimethylsilylethinyl-biphenyl (0.3 g) and finally, under cooling with ice, bis(2-oxo-3-oxazolidinyl) chlorophosphinic acid (0.29 g). After stirring for 18 hours the solvents were removed under reduced pressure and the residue was taken up with ethylacetate. Washing with water and brine, drying with sodiumsulfate and evaporation of the solvent yielded 0.45 g of a yellow oil which was chromatographed on silica gel (eluent: hexane:ethylacetate 2:1) to yield 0.13 g (26%) of Compound No. 2.01.

EXAMPLE 3

This Example illustrates the preparation of Compound No. 1.72.

To NaH (46 mg) in 5 ml dry THF at 0-5° C. was added 2-N-formylamino-4′-(propin-1-yl)-biphenyl (0.3 g) in 10 ml dry THF. The reaction was kept at this temperature for 1 hour and afterwards 1-methyl-3-trifluoromethyl-4-chlorocarbonyl-pyrazol (0.372 g) was added. The resultant suspension was stirred at room temperature overnight, poured into brine and extracted with ethylacetate. The solvent was evaporated and the the residue was taken into methanol and sodiummethylate (10 mg) was added. After 30 minutes the mixture was neutralised with diluted HCl, extracted with ethylacetate and washed until neutral. Chromatographic purification on silica gel (eluent: ethylacetate:hexane 1:2) and recrystallisation from toluene:hexane (4:1) yielded 0.169 g of Compound No. 1.72.

EXAMPLE 4

This Example illustrates the preparation of 2- amino4′-(trimethylsilyl)ethinyl-biphenyl (Compound No.12.02) and 2-amino-4′-ethinyl-biphenyl (Compound No.12.01) using a preparation according to Method F above.

To 2.5 g 2-amino-4′-bromo-biphenyl (WO0264562) in piperidine (25 ml) under nitrogen were added in sequence CuI (0.1 g), bis(triphenylphosphino)palladium dichloride (0.35 g) and trimethylsilylacetylene (2.8 ml). The mixture was stirred for 22 hours at room temperature and for a further 26 hours at 60° C. After cooling the reaction mixture was diluted with water and extracted with ethylacetate. Then the organic phase was washed with water and dried over sodium sulfate. After evaporation of the solvents in vacuum the mixture was chromatographed on silica gel (hexane:ethylacetate 9:1) to yield 2- amino-4′-(trimethylsilyl)ethinyl-biphenyl (2 g) (Compound No.12.02).

1.4 g of this compound was dissolved in methanol (40 ml) and potassium carbonate (0.9 g) was added with cooling. The resultant suspension was stirred for 2 hours, poured on ice-water and the precipitate formed was filtered off, washed thoroughly with water and dried to obtain 2-amino-4′-ethinyl-biphenyl (0.9 g) (Compound No.12.01) as light tan crystals.

EXAMPLE 5

This Example illustrates the preparation of 2-N-fonnylamino-4′-(propin-1-yl)-biphenyl (Compound No.12.16)

N-formylamino-4′bromo-biphenyl (3.5 g) (J. Chem. Soc. 1957, 4), tributyltin(propinyl-1) (5 g) (commercial from Aldrich), tetralis(triphenylphosphine)palladium (0.37 g) were combined in toluene (200 ml) under nitrogen and heated to reflux for 16 hours. The resultant dark mixture was diluted with water and extracted with ethyl acetate. The organic phase was washed with water, dried over sodium sulfate and the solvents were evaporated at reduced pressure. The residue was taken into acetonitrile and washed repeatedly with hexane. After removal of the acetonitrile at reduced pressure and chromatography of the residue with silicagel (eluent:hexane ethylacetate 2:1) 2-N-formylamino-4′-(propin-1-yl)-biphenyl (Compound No.12.16) (1.57 g) was obtained as a light yellow powder.

EXAMPLE 6

This Example illustrates the preparation of 2-amino-4′(2,2-dichloro)ethylene-biphenyl (Compound No. 12.07) and 2-amino-4′(chloroethinyl)-biphenyl (Compound No 12.04.

a) Preparation of 2-nitro4′(2,2-dichloro)ethylene-biphenyl.

To 2-nitro-4′formyl-biphenyl (2 g) (WO 95 03290) (prepared by Pd-catalysed coupling of 2-bromonnitrobenzene with 4-formyl-phenyl-boronic acid) in ethanol (70 ml) was added hydrazine hydrate (95%) (1.32 g) and the resultant mixture was then refluxed for 5 hours. The solvent was evaporated to dryness under reduced pressure, the residue was suspended in DMSO (30 ml) and then ammonia (25%) (3 ml),and freshly prepared CuCd (80 mg) were sequentially added and finally tetrachlorometane (3.8 g) was dropped in under cooling with water. The mixture was stirred at room temperature for 24 hours and the resultant green suspension was poured into water, extracted with dichloromethane, washed with water and dried over sodium sulfate. Evaporation of the solvent and chromatography of the residue over silicagel (eluent:hexane:ethylacetate 4:1) yielded 2-nitro-4′(2,2-dichloro)ethylene-biphenyl (0.8 g), m.p. 58-59° C.

b) Preparation of 2-amino-4′(2,2-dichloro)ethylene-biphenyl.

2-Nitro-4′(2,2-dichloro)ethylene-biphenyl (0.76 g) from step (a) was dissolved in 50% ethanol (30 ml) and heated to reflux. Then 2N HCl (0.3 ml) in 50% ethanol (10 ml) was added dropwise. The reaction mixture was held at reflux for 4 hours, cooled to room temperature and filtered. The filtrate was-neutralised with sodium bicarbonate, extracted twice with ethylacetate and the organic phase was dried over sodium sulfate. Evaporation of the solvent under reduced pressure yielded 2-amino-4′(2,2-dichloro)ethylene-biphenyl (0.62 g) (Compound No. 12.07).

c) 2-Amino-4′(2,2-dichloro)ethylene-biphenyl (3 g) was dissolved in 150 ml dimethyl sulfoxide in which 0.9 g KOH (85%, powder) has been suspended. The mixture was stirred over night at room temperature, diluted with excess of water and extracted twice with ethyl acetate and the organic phase was dried over sodium sulfate. Evaporation of the solvent under reduced pressure and chromatography of the residue over silicagel (eluent:hexane:ethylacetate 4:1) yielded 2.5 g 2-amino-4′(2,2-dichloro)ethylene-biphenyl as a tan coloured solid.

EXAMPLE 7

This Example illustrates the preparation of Compound Number 12.18.

Step A: 2-Nitro-(4′-trimethvlsilyl)-biphenyl

2-Bromo-nitrobenzene (0.86 g), 4-(trimethylsilyl)phenylboronic acid (1 g) and bis-(triphenylphosphine)-palladiumdichloride (0.3 g) were dissolved in dimethoxyetane (35 ml) and then a solution of sodium bicarbonate (1.3 g) dissoved in water (5 ml) was added dropwise. The mixture was heated for 3 hours (80° C. bath temperature), cooled to room temperature, poured on to ethyl acetate:water::1:1 (300 ml) and suction filtered. The organic phase was separated, dried over sodium sulfate and the solvent was removed. The resultant residue (1.58 g of a dark oil) was chromatographed on silica gel (eluent:hexane:ethyl acetate::4:1) to yield a yellow oil (1.12 g). This compound was used in Step B.

Step B: 2-Amino-(4′-trimethylsilyl)-biphenyl Compound 12.18]

The compound obtainedfrom step A above (0.955 g) and ammonium formiate (1.86 g) were dissolved in methanol (30 ml) and purged with nitrogen. To this solution, Pd (100 mg; 10% on carbon) was added, in 2 portions. After stirring at room temperature for 15 hours, the reaction mixture was filtered and the solvent was evaporated.

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I)

Working procedures for preparing formulations of the compounds of formula I such as Emulsifiable Concentrates, Solutions, Granules, Dusts and Wettable Powders are described in WO97/33890.

BIOLOGICAL EXAMPLES: FUNGIClDAL ACTIONS Example B-1 Action Against Puccinia Recondita/wheat (Brownrust on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (1×10⁵ uredospores/ml) on the test plants. After an incubation period of 2 days at 20° C. and 95% r.h. the plants are kept in a greenhouse for 8 days at 20° C. and 60% r.h. The disease incidence is assessed 10 days after inoculation.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.22, 1.24, 1.33, 1.56, 1.57, 1.60, 1.66, 1.67, 1.69, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.138, 1.139, 1.151, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, 1.252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.56, 3.66, 3.69, 3.250, 9.01, 9.06, 9.15, 9.21, 9.41, 9.50, 9.53, 9.59, 15.25, 15.26 and 15.28.

Example B-2 Action Against Podosphaera Leucotricha/apple (Powdery Mildew on Apple)

5 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22° C. and 60% r.h. under a light regime of 14/10 hours (light/dark) the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds. 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.24, 1.33, 1.35, 1.36, 1.56, 1.57, 1.66, 1.67, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.139, 1.151, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, 1.252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.35, 3.56, 3.66, 3.69, 3.250, 9.01, 9.06, 9.15, 9.21, 9.41, 9.50, 9.53, 9.59, 9.62, 15.25, 15.26 and 15.28.

Example B-3 Action Against Venturia Inaegualis/apple (Scab on Apple)

4 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% r.h. the plants are placed for 4 days at 21° C. and 60% r.h. in a greenhouse. After another 4 day incubation period at 21° C. and 95% r.h. the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds. 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.18, 1.19, 1.24, 1.33, 1.56, 1.57, 1.66, 1.67, 1.69, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.138, 1.152, 1.154, 1.155, 1.251, 1.252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.56, 3.66, 3.69, 9.01, 9.06, 9.15, 9.21, 9.50 and 9.59.

Example B-4 Action Against Erysiphe Graminis/barley (Powdery Mildew on Barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20° C./18° C. (day/night) and 60% r.h. in a greenhouse the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.24, 1.33, 1.35, 1.36, 1.56, 1.57, 1.66, 1.67, 1.70, 1.77, 1.78, 1.106, 1.107, 1.152, 1.155, 1.251, 1.252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.35, 3.56, 3.66, 3.69, 3.250, 9.01, 9.06, 9.15, 9.21, 9.41, 9.50 and 9.59.

Example B-5 Action Against Botrytis Cinerea/grape (Botrytis on Grapes)

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (1×10⁶ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% r.h. in a greenhouse the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08 and 1.10.

Example B-6 Action Against Botrytis Cinerea/tomato (Botrytis on Tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (1×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% r.h. in a growth chamber the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.24, 1.33, 1.36, 1.56, 1.57, 1.66, 1.67, 1.69, 1.70, 1.77, 1.78, 1.106, 1.107, 1.138, 1.139, 1.152, 1.155, 1.251, 1.252, 2.01, 2.66, 3.01, 3.08, 3.12, 3.66, 3.69, 3.250, 9.06, 9.15, 9.21, 9.41, 9.50 and 9.59.

Example B-7 Action Against Septoria Nodorum/wheat (Setoria Leaf Spot on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5×10⁵ conidialml) on the test plants. After an incubation period of 1 day at 20° C. and 95% r.h. the plants are kept for 10 days at 20° C. and 60% r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08 and 1.10.

Example B-8 Action Against Helminthosporium Teres/barley (Net Blotch on Barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3×10⁴ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% r.h. in a greenhouse the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.22, 1.24, 1.33, 1.36, 1.35, 1.56, 1.57, 1.60, 1.66, 1.67, 1.69, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.138, 1.139, 1.151, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, 1.252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.35, 3.56, 3.66, 3.69, 9.01, 9.06, 9.15, 9.21, 9.41, 9.50, 9.53, 9.59, 9.62, 15.25, 15.26 and 15.28.

Example B-9 Action Against Alternaria Solani/tomato (Early Blight on Tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2×10⁵ conidia/ml) on the test plants. After an incubation period of 3 days at 20° C. and 95% r.h. in a growth chamber the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.13, 1.15, 1.16, 1.19, 1.22, 1.24, 1.33, 1.35, 1.36, 1.56, 1.57, 1.67, 1.69, 1.70, 1.77, 1.78, 1.81, 1.107, 1.151, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, 1.252, 2.01, 3.01, 3.08, 3.12, 3.32, 3.35, 3.56, 3.69, 9.01, 9.06, 9.15, 9.41, 9.50, 9.62 and 15.26.

Example B-10 Action Against Uncinula Necator/grape (Powdery Mildew on Grapes)

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 26° C. and 60% r.h. under a light regime of 14/10 hours (light/dark) the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.18, 1.19, 1.24, 1.33, 1.56, 1.57, 1.60, 1.66, 1.67, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.138, 1.139, 1.151, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, 1.252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.32, 3.56, 3.66, 3.69, 3.250, 9.01, 9.06, 9.15, 9.41, 9.50, 9.53 and 9.59.

Example B-11 Action Against Septoria Tritici/wheat (Septoria Leaf Spot on Wheat)

2 week old wheat plants cv. Riband are treated with the formulated test compound (0.2% active ingredient) in a spray chamber. One day after application, wheat plants are inoculated by spraying a spore suspension (10×10⁵ conidia/ml) on the test plants. After an incubation period of I day at 23° C. and 95% r.h., the plants are kept for 16 days at 23° C. and 60% r.h. in a greenhouse. The disease incidence is assessed 18 days after inoculation.

Compounds 1.10, 1.03, 1.09, 1.70, 1.69, 3.01, 1.67, 1.66, 3.66, 9.59, 3.69, 1.33, 2.66, 9.06, 3.08, 1.77, 1.78, 1.56, 1.57, 1.138, 1.139, 1.12, 1.18, 1.106, 1.107, 9.53, 3.32, 1.151, 1.152, 1.252, 1.155, 9.41, 3.56, 1.13, 3.12, 9.21, 1.250, 1.19 and 3.18. each show good activity in this test (<20% disease incidence). 

1. A compound of formula (I):

where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and suphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by one, two or three groups R^(y); R¹ is hydrogen, formyl, CO—C₁₋₄ alkyl, COO—C₁₋₄ alkyl, C₁₋₄ alkoxy(C₁₋₄)alkylene, CO—C₁₋₄ alkylenoxy(C₁₋₄)alkyl, propargyl or allenyl; R², R³, and R⁴ are each, independently, hydrogen, halogen, methyl or CF₃; R⁵ is hydrogen or fluorine; each R⁶ is, independently, halogen, methyl or CF₃; R⁷ is (Z)_(m)C≡C(Y¹), or (Z)_(m)C(Y¹)═C(Y²)(Y³); each R^(y) is, independently, halogen, C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy(C₁₋₃)alkylene or cyano; X is 0 or S; Y¹, Y² and Y³ are each, independently, hydrogen, halogen, C₁₋₆ alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio, C₁₋₄ alkylamino, di(C₁₋₄)alkylamino, C₁₋₄ alkoxycarbonyl, C₁₋₄ alkylcarbonyloxy and tri(C₁₋₄)alkylsilyl], C₂₋₄ alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C₂₋₄ alkynyl [optionally substituted by one or more substituents each independently selected from halogen], C₃₋₇ cycloalkyl [optionally substituted by one or more substituents each independently selected from halogen, C₁₋₄ alkyl and C₁₋₄ haloalkyl] or tri(C₁₋₄)alkylsilyl; Z is C₁₋₄ alkylene [optionally substituted by one or more substituents each independently selected from hydroxy, cyano, C₁₋₄ alkoxy, halogen, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, COOH and COO—C₁₋₄ alkyl]; m is 0 or 1; and n is 0, 1 or
 2. 2. A compound of formula (I) as claimed in claim 1 where Het is pyrazole, pyrrole, thiophene, furan, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 5,6-dihydropyran or 5,6-dihydro-1,4-oxathiine.
 3. A compound of formula (I) as claimed in claim 1 where R¹ is hydrogen, propargyl, allenyl, formyl, COMe, COEt or COCH₂OMe.
 4. A compound of formula (I) as claimed in claim 1, where Y¹, Y² and Y³ are, independently, hydrogen, halogen, C₁₋₆ alkyl, C₁₋₃ haloalkyl, C₁₋₄(haloalkoxy)C₁₋₄alkyl, C₁₋₄(haloalkylthio)C₁₋₄ alkyl, trimethylsilyl, C₂₋₄ alkenyl, C₂₋₄ haloalkenyl or C₃₋₆ cycloalkyl (optionally substituted by one or more substituents each independently selected from halogen and C₁₋₂ alkyl).
 5. A compound of formula (I) as claimed in claim 1, where m=0.
 6. A compound of formula (I) as claimed in claim 1, where Z is C₁₋₂ alkylene [which may be optionally substituted by one or more substituents each independently selected from halogen, C₁₋₄ haloalkyl and C₁₋₄ haloalkoxy].
 7. A compound of formula (I) as claimed in claim 1, where R⁷ is in the 4′ position.
 8. A compound of formula (I) as claimed in claim 1, where n=0.
 9. A compound of formula (II):

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n are as defined in claim 1; provided that when R¹, R², R³, R⁴ and R⁵ are each hydrogen and n is 0 then R⁷ is not CH═C(H)CH₂CO₂H.
 10. A compound of formula (III):

where R², R³, R⁴, R⁵, R⁶, R⁷ and n are as defined in claim 1 and Hal is bromo, chloro or iodo; provided that the compound is not a compound of formula (IIIa) according to Table
 0. 11. A composition for controlling microorganisms and preventing attack and infestation of plants therewith, wherein the active ingredient is a compound of formula (I) as claimed in claim 1 together with a suitable carrier.
 12. A method of controlling or preventing infestation of cultivated plants by phytopathogenic microorganisms by application of a compound of formula (I) as claimed in claim 1 to plants, to parts thereof or the locus thereof. 